CN105186018A - Fuel cell system and operating method of a fuel cell - Google Patents

Fuel cell system and operating method of a fuel cell Download PDF

Info

Publication number
CN105186018A
CN105186018A CN201510726171.7A CN201510726171A CN105186018A CN 105186018 A CN105186018 A CN 105186018A CN 201510726171 A CN201510726171 A CN 201510726171A CN 105186018 A CN105186018 A CN 105186018A
Authority
CN
China
Prior art keywords
oxidant gas
gas flow
flow paths
water
fuel cell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510726171.7A
Other languages
Chinese (zh)
Other versions
CN105186018B (en
Inventor
长谷川茂树
安藤雅树
滨田研一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyota Motor Corp
Original Assignee
Toyota Motor Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyota Motor Corp filed Critical Toyota Motor Corp
Publication of CN105186018A publication Critical patent/CN105186018A/en
Application granted granted Critical
Publication of CN105186018B publication Critical patent/CN105186018B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04828—Humidity; Water content
    • H01M8/0485—Humidity; Water content of the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04104—Regulation of differential pressures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04291—Arrangements for managing water in solid electrolyte fuel cell systems
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/04492—Humidity; Ambient humidity; Water content
    • H01M8/045—Humidity; Ambient humidity; Water content of anode reactants at the inlet or inside the fuel cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/04492—Humidity; Ambient humidity; Water content
    • H01M8/04507—Humidity; Ambient humidity; Water content of cathode reactants at the inlet or inside the fuel cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/04492—Humidity; Ambient humidity; Water content
    • H01M8/04529—Humidity; Ambient humidity; Water content of the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04746—Pressure; Flow
    • H01M8/04753—Pressure; Flow of fuel cell reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04746—Pressure; Flow
    • H01M8/04783—Pressure differences, e.g. between anode and cathode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • H01M8/04126—Humidifying
    • H01M8/04149—Humidifying by diffusion, e.g. making use of membranes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

A fuel cell system operates under at least one of the conditions of no humidity or high temperature, and an operating method thereof, are characterized in that a fuel cell has a fuel gas flow path and an oxidant gas flow path arranged such that fuel gas and oxidant gas flow in opposite directions, a determining apparatus that determines the amount of water near the oxidant gas flow path inlet, and a fuel gas control apparatus which increases the amount of water near the oxidant gas flow path inlet by increasing the fuel gas flowrate and/or reducing the fuel gas pressure if it is determined in the determining apparatus that the amount of water near the oxidant gas flow path inlet is insufficient.

Description

The method of operation of fuel cell system and fuel cell
The application is the divisional application that name is called " method of operation of fuel cell system and fuel cell ", international filing date is on March 26th, 2009, international application no is PCT/IB2009/005332, national applications number is the application for a patent for invention of 200980100116.X.
Technical field
The present invention relates to the method for operation that a kind of anti-sealing is distributed in fuel cell system on the surface of monocell and fuel cell unevenly.
Background technology
Fuel cell is by being supplied to two electrodes be electrically connected by fuel and oxidant and electrochemically oxygenated fuel and directly chemical energy is become electric energy.Generate electricity different from heat, fuel cell efficiency in conversion of energy is high, this is because fuel cell does not limit by Carnot cycle.Fuel cell is formed by the heap of multiple monocell usually, and each described monocell is basic to be made up of membrane electrode assembly (MEA), and in described membrane electrode assembly, dielectric film is clipped between pair of electrodes.Among fuel cell, using polymer dielectric film as the polymer electrolyte fuel cells of dielectric film as portable power supply with for especially attractive in the power supply of moveable object, this is because polymer electrolyte fuel cells can easily manufacture less and can operate at low temperatures.
In polymer electrolyte fuel cells, when hydrogen is used as fuel, there is the reaction in following formula (1) at anode (that is, fuel electrode) place.
H 2→2H ++2e -(1)
As the result of above expression formula (1), the electronics that discharges is through external circuit, at these electronics of described external circuit place in the acting of external applied load place, and then arrives negative electrode (that is, oxidizing agent pole).Here, the proton produced by expression formula (1) arrives negative electrode from anode movement by polymer dielectric film in from the hydration status of electric osmose.
And, when oxygen is used as oxidant, there is the reaction in expression formula (2) at negative electrode place.
2H ++(1/2)O 2+2e -→H 2O(2)
The water produced at negative electrode place is mainly through gas diffusion layers, and water is discharged from fuel cell after this.Like this, fuel cell is the cleaner power sources of a discharge water.
If have too much water to be discharged (in this manual, term " water " is for wide significance, and thus also comprise moisture and analog), then the water of condensation in a fuel cell can block the space in catalyst layer or gas diffusion layers, and in extreme circumstances, even barrier gas flow path, and thus hinder the supply of gas, stop the gas of the q.s for generating electricity to arrive catalyst layer, this reduces causing the output of fuel cell.And if do not have enough water in a fuel cell, then resistance in increasing, causes output and the decrease of power generation of fuel cell equally.For solving this problem, be previously developed the various technology of following explanation.
Japanese Patent Application Publication No.2002-352827 (JP-A-2002-352827) describes the technology relating to a kind of fuel cell system, described fuel cell system comprises: I) water yield decision maker, it is still not enough for judging the hypervolia in fuel cell; And II) gas delivery volume control device, its for based on from water yield decision maker about the hypervolia in fuel cell or not enough result of determination, control to be supplied to the oxygen of fuel cell and/or the gas delivery volume of hydrogen.
Japanese Patent Application Publication No.2006-210004 (JP-A-2006-210004) describes the technology relating to a kind of fuel cell system, described fuel cell system comprises: I) air capacity adjusting device, it is for regulating the air capacity flowed in oxidant gas flow paths; II) decision maker, it is for judging whether dielectric film becomes dry; And III) control device, it, for when judging that dielectric film becomes dry, controls the pressure of the air flowed in oxidant gas flow paths, to make the pressure of described air higher than the pressure of the air in during normal running.
The disclosed Japanese Translation of PCT application No.6-504403 (JP-A-6-504403) describes following technology: its water for being removed in negative electrode by the steam partial pressure in fuel metering gas, thus makes water or steam move to anode from negative electrode by dielectric film.
Japan Patent No.3736475 describes following technology: it is for by making the water flocculation in oxidant gas and recovery and promoting that the water yield is supplied to fuel gas flow path intake section via dielectric film.This realizes in the following way: arrange fuel gas flow path and oxidant gas flow paths, to make fuel gas and oxidant gas reciprocally flow in a fuel cell; And coolant path is set, for cooling oxidant gas flow paths exit portion.
Japanese Patent Application Publication No.2001-6698 (JP-A-2001-6698) describes following technology: it suppresses steam to diffuse in oxidant gas for the rate of drying by reducing in oxidant gas flow paths.This is realized by following layout: when fuel battery operation, make the temperature of oxidant gas flow paths porch lower than the temperature in oxidant gas flow paths exit, and the gas that the gas of the diffusion layer of oxidant gas flow paths porch spreads lower than oxidant gas flow paths exit is spread.
When supplying the fuel battery operation of fuel gas and the oxidant gas having non-humidification, that is, during the operation of non-humidification, water trends towards on the surface of the monocell being distributed in fuel cell unevenly.That is, the region near oxidant gas flow paths entrance trends towards becoming dry, and the region near oxidant gas flow paths outlet trends towards becoming wet.Therefore, be necessary that to make the water yield on the surface of monocell as possible even.When the temperature of membrane electrode assembly is higher, that is, 70 DEG C or higher time, be also like this.Both the technology illustrated in JP-A-2002-352827 and JP-A-2006-210004 all comprise the device for solving this problem, that is, these two kinds of technology all judge the hypervolia of whole fuel cell or not enough, and based on this judgement adjustments of gas.But these two kinds of technology all do not consider the uneven distribution of water on the surface of monocell.Therefore, when there being water too many or very little on the surface of monocell, these two kinds of technology are all considered to invalid.Especially, in the control device illustrated in JP-A-2006-210004, the device for solving this problem by increasing air pressure is considered to owing to increasing air compressor output and has the shortcoming reducing fuel efficiency.The technology illustrated in JP-A-6-504403, the technology illustrated in Japan Patent No.3736475 and the technology illustrated in JP-A-2001-6698 all have the device for solving this problem, and it comprises the water making mainly to assemble near the outlet of oxidant gas flow paths and arrives fuel gas flow path through dielectric film.Especially, the technology illustrated in Japan Patent No.3736475 and the technology illustrated in JP-A-2001-6698 all have the device for solving this problem, it comprise make water from oxidant gas flow paths outlet near → fuel gas flow path entrance near → fuel gas flow path outlet near → oxidant gas flow paths entrance near circulate, this is because oxidant gas flow paths and fuel gas flow path are contrary.But, even by the technology illustrated in JP-A-6-504403, the technology illustrated in Japan Patent No.3736475 and the technology that illustrates in JP-A-2001-6698, all do not consider for judging the decision maker whether water yield is too much or not enough, and for the control device of adjustments of gas based on the judgement made by described decision maker.And the technology illustrated in JP-A-6-504403 wants the water logging (flooding) prevented in oxidant gas flow paths, but do not want to prevent the region near oxidant gas flow paths entrance from becoming dry.
Summary of the invention
In view of the above problems, the present invention thus provide a kind of anti-sealing to be distributed in the method for operation of fuel cell system on the surface of monocell and fuel cell unevenly.
Therefore, a first aspect of the present invention relates to a kind of fuel cell system being provided with fuel cell, described fuel cell has heap, described heap has monocell, described monocell comprises membrane electrode assembly, in described membrane electrode assembly, polymer dielectric film is clipped between pair of electrodes, and fuel gas and oxidant gas are supplied to fuel cell by described membrane electrode assembly, and in I) do not have moist condition or II) temperature of membrane electrode assembly operates under at least one condition in the condition of at least 70 DEG C.Fuel cell has fuel gas flow path on the side of membrane electrode assembly, and on the opposite side of membrane electrode assembly, there is oxidant gas flow paths, and fuel gas flow path and oxidant gas flow paths are arranged so that fuel gas and oxidant gas flow along contrary direction.Fuel cell system comprises: the decision maker judging the water yield near oxidant gas flow paths entrance; With fuel gas control device, if judge the water shortage near oxidant gas flow paths entrance by described decision maker, then described fuel gas control device is increased in the water yield near oxidant gas flow paths entrance by increasing fuel gas flow and/or reducing fuel gas pressure.
By the fuel cell system with this structure, water near oxidant gas flow paths outlet has been transported near fuel gas flow path entrance by polymer dielectric film after, by the more water yield in fuel gas being transported near fuel gas flow path outlet, the more water yield can be transported near oxidant gas flow paths entrance by polymer dielectric film near fuel gas flow path outlet.Therefore, the water yield near oxidant gas flow paths entrance and the water yield near oxidant gas flow paths outlet can be regulated, described oxidant gas flow paths entrance trends towards becoming dry in the prior art, and described oxidant gas flow paths outlet trends towards becoming wet in the prior art.As a result, when can work as under not moist condition and/or under the condition of high temperature, anti-sealing is distributed on the surface of monocell unevenly.And fuel cell system of the present invention has decision maker, so the deficiency of the water yield near oxidant gas flow paths entrance can be determined exactly.
Fuel cell system can also comprise: the decision maker judging the water yield near oxidant gas flow paths entrance and/or near oxidant gas flow paths outlet, with with at least one in lower device: I) fuel gas control device, if judge the water shortage near oxidant gas flow paths entrance and/or the hypervolia near oxidant gas flow paths outlet in described decision maker, then described fuel gas control device is by increasing fuel gas flow and/or reducing fuel gas pressure and promote that the water near oxidant gas flow paths outlet is transported near oxidant gas flow paths entrance via fuel gas flow path, thus the water yield be increased near oxidant gas flow paths entrance and the water yield reduced near oxidant gas flow paths outlet, or II) oxidant gas control device, if to judge in described decision maker near oxidant gas flow paths entrance and/or water shortage near oxidant gas flow paths outlet, then described oxidant gas control device reduces the water yield of being taken out of from battery by oxidant gas and increases the water yield that can be transported to fuel gas flow path entrance side from oxidant gas flow paths outlet side by reducing oxidizer gas flow rate and/or increase oxidant gas pressure.
By the fuel cell system with this structure, water near oxidant gas flow paths outlet has been transported near fuel gas flow path entrance by polymer dielectric film after, by the more water yield in fuel gas being transported near fuel gas flow path outlet, the more water yield can be transported near oxidant gas flow paths entrance by polymer dielectric film near fuel gas flow path outlet.Therefore, the water yield near oxidant gas flow paths entrance and the water yield near oxidant gas flow paths outlet can be regulated, described trending towards in the prior art near oxidant gas flow paths entrance becomes dry, and described trending towards in the prior art near oxidant gas flow paths outlet becomes wet.As a result, when can work as under not moist condition and/or under the condition of high temperature, anti-sealing is distributed on the surface of monocell unevenly.And according to the present invention, by reducing to be taken away by oxidant gas and being discharged into the water yield of the outside of fuel cell system of the present invention, water can be gathered near oxidant gas flow paths outlet.In addition, fuel cell system of the present invention has decision maker, so can determine the water shortage or too much near oxidant gas flow paths entrance and exit exactly.
And, in above-mentioned fuel cell system, decision maker can be decision maker A, described decision maker A measures the resistance value of whole fuel cell, and when 105% of the minimum value of the resistance measured in advance of the monocell at each temperature that this resistance value exceedes in multiple temperature and/or heap, judge the water shortage near oxidant gas flow paths entrance and/or the water shortage near oxidant gas flow paths outlet.
The water shortage that the fuel cell system with this structure can use the simple method of the resistance value measuring whole fuel cell to determine exactly near oxidant gas flow paths entrance and exit.
And, in above-mentioned fuel cell system, decision maker can be decision maker B, described decision maker B measures resistance value and the voltage of whole fuel cell, and 105% of the minimum value (wet state) when the resistance measured in advance at each temperature that resistance value is less than in multiple temperature, and when voltage is less than 95% of the maximum of the voltage measured in advance of monocell at each temperature in multiple temperature and/or heap, judge the hypervolia near oxidant gas flow paths entrance and/or the hypervolia near oxidant gas flow paths outlet.
The hypervolia that the fuel cell system with this structure can use the simple method of the voltage measuring whole fuel cell to determine exactly near oxidant gas flow paths entrance and exit.
And, in above-mentioned fuel cell system, decision maker can be decision maker C, the pressure drop of the oxidant gas of oxidant gas flow paths is flow through in described decision maker C measurement, and when pressure drop is less than 105% of the minimum value of the pressure drop of measuring in advance of the oxidant gas flowing through oxidant gas flow paths, judge the water shortage near oxidant gas flow paths entrance and/or the water shortage near oxidant gas flow paths outlet.
The fuel cell system with this structure can use the water shortage measured the simple method flowing through the pressure drop of the oxidant gas of oxidant gas flow paths and determine exactly near oxidant gas flow paths entrance and exit.
And, in above-mentioned fuel cell system, decision maker can be decision maker D, the pressure drop of the oxidant gas of oxidant gas flow paths is flow through in described decision maker D measurement, and when pressure drop exceedes 105% of the maximum of the pressure drop of measuring in advance of the oxidant gas flowing through oxidant gas flow paths, judge the hypervolia near oxidant gas flow paths entrance and/or the hypervolia near oxidant gas flow paths outlet.
The fuel cell system with this structure can use the hypervolia measured the simple method flowing through the pressure drop of the oxidant gas of oxidant gas flow paths and determine exactly near oxidant gas flow paths entrance and exit.
And, in above-mentioned fuel cell system, can be provided with fuel gas pressure adjuster valve near fuel gas flow path outlet, and fuel gas control device can be the fuel gas pressure control device reducing fuel gas pressure by regulating this fuel gas pressure adjuster valve.
The fuel cell system with this structure can reduce fuel gas pressure by the simple operations of fuel metering gas pressure adjuster valve.
And in above-mentioned fuel cell system, fuel gas pressure control device can fuel metering gas pressure adjuster valve, is more than or equal to atmospheric pressure to be reduced to by fuel gas pressure and to be less than or equal in the scope of 0.3MPa.
Owing to maintaining the water yield enough in fuel gas by being remained in suitable scope by fuel gas pressure, the fuel cell system with this structure can increase the water yield that can be transported to oxidant gas flow paths by dielectric film.
And, in above-mentioned fuel cell system, oxidant gas feedway can also be provided with, and oxidant gas control device can be the oxidizer gas flow rate control device reducing oxidizer gas flow rate by regulating oxidant gas feedway.
The fuel cell system with this structure can reduce oxidizer gas flow rate by regulating the simple operations of oxidant gas feedway.
And in above-mentioned fuel cell system, oxidizer gas flow rate control device can regulate oxidant gas feedway, be more than or equal to 1.0 so that the stoichiometric proportion of oxidant gas is reduced to and is less than or equal in the scope of 3.0.
Due to by the stoichiometric proportion of oxidant gas is reduced to the water yield that in suitable scope, minimizing is taken out of from fuel cell by oxidant gas, the fuel cell system with this structure can reduce the water yield that can be transported to oxidant gas flow paths by dielectric film.
And, above-mentioned fuel cell system can also comprise the fuel gas feeding device of fuel gas supply to fuel cell, and fuel gas control device can be the fuel gas volume control device being increased fuel gas flow by fuel metering gas supply device.
The fuel cell system with this structure can increase fuel gas flow by the simple operations of fuel metering gas supply device.
And in above-mentioned fuel cell system, fuel gas volume control device can fuel metering gas supply device, is more than or equal to 1.0 the stoichiometric proportion of fuel gas to be increased to and is less than or equal in the scope of 10.
Due to by the stoichiometric proportion of fuel gas being increased to enough water yields of maintaining in fuel gas in suitable scope and not making polymer dielectric film become dry, the fuel cell system with this structure can increase the water yield that can be transported to oxidant gas flow paths by dielectric film.
And, above-mentioned fuel cell system can also comprise oxidant gas pressure adjuster valve, it to be arranged near oxidant gas flow paths outlet and to regulate the pressure of oxidant gas, and oxidant gas control device can be the oxidant gas pressure control device increasing oxidant gas pressure by regulating oxidant gas pressure adjuster valve.
The fuel cell system with this structure can increase oxidant gas pressure by regulating the simple operations of oxidant gas pressure adjuster valve.
And in above-mentioned fuel cell system, oxidant gas pressure control device can regulate oxidant gas pressure adjuster valve, be more than or equal to atmospheric pressure so that oxidant gas pressure is increased to and is less than or equal in the scope of 0.3MPa.
Due to by oxidant gas pressure being remained on the water yield that in suitable scope, minimizing is taken out of from fuel cell by oxidant gas, the fuel cell system with this structure can reduce the water yield that can be transported to oxidant gas flow paths by dielectric film.
And above-mentioned fuel cell system can also comprise: fuel gas control device; Oxidant gas control device; Decision maker A and/or decision maker C; Decision maker B and/or decision maker D; Water conveying promotes to control starting device A, and after judging the water shortage near oxidant gas flow paths entrance by decision maker A and/or C, described water conveying promotes that controlling starting device A operates fuel gas control device one or many; Water conveying promotes to control arresting stop A, after water conveying promotes that controlling starting device A operates fuel gas control device, after judged the water shortage near oxidant gas flow paths outlet by decision maker A and/or C, described water conveying promotes that controlling arresting stop A stops fuel gas control device; Water conveying inhibitory control starting device A, after water conveying promotes that controlling arresting stop A stops fuel gas control device, described water conveying inhibitory control starting device A operating oxidizer gas control equipment one or many; Water conveying inhibitory control arresting stop A, after judged the hypervolia near oxidant gas flow paths outlet by decision maker B and/or D, described water conveying inhibitory control arresting stop A stops all elements of oxidant gas control device; And the final decision maker A of the not enough water yield.After water conveying inhibitory control arresting stop A stops all elements of oxidant gas control device, if judge the water shortage near oxidant gas flow paths entrance by decision maker A and/or C, then the final decision maker A of the not enough water yield makes water carry promotion to control starting device A and again operates fuel gas control device, and if judge that the water yield near oxidant gas flow paths entrance is not not enough by decision maker A and/or C, then the final decision maker A of the not enough water yield continues operation of fuel cells.
By the fuel cell system with this structure, when judging the water shortage near oxidant gas flow paths entrance, after the conveying of use water promotes that controlling starting device A promotes that water is transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet, by using water conveying inhibitory control starting device A to be increased in the water yield near oxidant gas flow paths outlet, both not many also not suitable water yields very little can be maintained near oxidant gas flow paths entrance and exit.And, by fuel cell system of the present invention, can, based on the result from the final decision maker A of the not enough water yield, by again repeating series of steps, prevent the water in whole oxidant gas flow paths from distributing unevenly.
And, can comprise according to above-mentioned fuel cell system: fuel gas control device; Oxidant gas control device; Decision maker A and/or decision maker C; Decision maker B and/or decision maker D; Water conveying inhibitory control starting device B, after judging the water shortage near oxidant gas flow paths entrance by decision maker A and/or C, described water conveying inhibitory control starting device B operating oxidizer gas control equipment one or many; Water conveying inhibitory control arresting stop B, after water conveying inhibitory control starting device B operating oxidizer gas control equipment, after judged the hypervolia near oxidant gas flow paths outlet by decision maker B and/or D, described water conveying inhibitory control arresting stop B stops oxidant gas control device; Water conveying promotes to control starting device B, and after water conveying inhibitory control arresting stop B stops oxidant gas control device, described water conveying promotes that controlling starting device B operates fuel gas control device one or many; Water conveying promotes to control arresting stop B, and after judged the water shortage near oxidant gas flow paths outlet by decision maker A and/or C, described water conveying promotes to control all elements that arresting stop B stops fuel gas control device; And the final decision maker B of the not enough water yield.After water conveying promotes that controlling arresting stop B stops all elements of fuel gas control device, if judge the water shortage near oxidant gas flow paths entrance by decision maker A and/or C, then the final decision maker B of the described not enough water yield makes water carry inhibitory control starting device B operating oxidizer gas control equipment again, and if judge that the water yield near oxidant gas flow paths entrance is not not enough by decision maker A and/or C, then the final decision maker B of the described not enough water yield continues operation of fuel cells.
By the fuel cell system with this structure, when judging the water shortage near oxidant gas flow paths entrance, water is suppressed to be transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet by using water conveying inhibitory control starting device B, and assembled the water having q.s near oxidant gas flow paths outlet after, controlling starting device B promotes that water is transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet to use water conveying to promote, both not many also not suitable water yields very little can be maintained near oxidant gas flow paths entrance and exit.And, by fuel cell system of the present invention, can, based on the result from the final decision maker B of the not enough water yield, by again repeating series of steps, prevent the water in whole oxidant gas flow paths from distributing unevenly.
And above-mentioned fuel cell system can comprise: fuel gas control device; Oxidant gas control device; Decision maker A and/or decision maker C; Decision maker B and/or decision maker D; Promote to control starting device little over the conveying of many water, its operation fuel gas control device one or many; Promote to control arresting stop little over the conveying of many water, after promote to control starting device operation fuel gas control device little over the conveying of many water, after judged the water shortage near oxidant gas flow paths outlet by decision maker A and/or C, described conveying little over many water promotes that controlling arresting stop stops fuel gas control device; Water conveying inhibitory control starting device C, after promoting that controlling arresting stop stops fuel gas control device little over the conveying of many water, described water conveying inhibitory control starting device C operating oxidizer gas control equipment; Water conveying inhibitory control arresting stop C, after judged the hypervolia near oxidant gas flow paths outlet by decision maker B and/or D, described water conveying inhibitory control arresting stop C stops all elements of oxidant gas control device; Water conveying promotes to control starting device C, and after water conveying inhibitory control arresting stop C stops all elements of oxidant gas control device, described water conveying promotes that controlling starting device C operates fuel gas control device; And water conveying promotes to control arresting stop C.After water conveying promotes that controlling starting device C operates fuel gas control device, if judge the water shortage near oxidant gas flow paths outlet by decision maker A and/or C, then water conveying promotes that controlling arresting stop C makes water carry inhibitory control starting device C operating oxidizer gas control equipment again, and if judge that the water yield near oxidant gas flow paths outlet is not not enough by decision maker A and/or C, then described water conveying promotes that controlling arresting stop C stops fuel gas control device and continue operation of fuel cells.
By the fuel cell system with this structure, promote that controlling starting device makes the water yield near oxidant gas flow paths outlet suitably not enough by first using little over the conveying of many water, then use water conveying inhibitory control starting device C and suppress water to be transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet, and assembled the water having q.s near oxidant gas flow paths outlet after, controlling starting device C promotes that water is transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet to use water conveying to promote, both not many also not suitable water yields very little can be maintained near oxidant gas flow paths entrance and exit.And, just the catalyst layer of its original performance can not be maintained (such as once become wet when fuel cell system of the present invention comprises having, this catalyst layer: the small aperture wherein in catalyst layer is got clogged by oxidation catalyst wittingly) fuel cell time, fuel cell system of the present invention is especially effective, this is because this fuel cell system can not allow catalyst layer become wet.
And above-mentioned fuel cell system can comprise: fuel gas control device; Oxidant gas control device; Decision maker A and/or decision maker C; Decision maker B and/or decision maker D; Little over many water conveying inhibitory control starting device, its operating oxidizer gas control equipment one or many; Little over many water conveying inhibitory control arresting stop, after little over many water conveying inhibitory control starting device operating oxidizer gas control equipment, after judged the hypervolia near oxidant gas flow paths outlet by decision maker B and/or D, described little over many water conveying inhibitory control arresting stop stopping oxidant gas control device; Water conveying promotes to control starting device D, and after stopping oxidant gas control device little over many water conveying inhibitory control arresting stop, described water conveying promotes that controlling starting device D operates fuel gas control device; Water conveying promotes to control arresting stop D, and after judged the water shortage near oxidant gas flow paths outlet by decision maker A and/or C, described water conveying promotes to control all elements that arresting stop D stops fuel gas control device; Water conveying inhibitory control starting device D, after water conveying promotes that controlling arresting stop D stops all elements of fuel gas control device, described water conveying inhibitory control starting device D operating oxidizer gas control equipment; And water conveying inhibitory control arresting stop D.After water conveying inhibitory control starting device D operating oxidizer gas control equipment, if judge the hypervolia near oxidant gas flow paths outlet by decision maker B and/or D, then water conveying inhibitory control arresting stop D makes water carry promotion to control starting device D and again operates fuel gas control device, and if judge that the water yield near oxidant gas flow paths outlet is not too much by decision maker B and/or D, then water conveying inhibitory control arresting stop D stops oxidant gas control device and continues operation of fuel cells.
By the fuel cell system with this structure, make the water yield near oxidant gas flow paths outlet suitably too much by first using little over many water conveying inhibitory control starting device, then water conveying is used to promote control starting device D and promote that water is transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet, and then use water conveying inhibitory control starting device D is increased in the water yield near oxidant gas flow paths outlet, both not many also not suitable water yields very little can be maintained near oxidant gas flow paths entrance and exit.And, when fuel cell system of the present invention comprise have just can not maintain its original performance once become dry dielectric film (such as, cross carbon fluoro sulfonate dielectric film) fuel cell time, fuel cell system of the present invention is especially effective, this is because this fuel cell system can not allow dielectric film become dry.
Another aspect of the present invention relates to a kind of method of operation of fuel cell, described fuel cell has heap, described heap has monocell, described monocell comprises membrane electrode assembly, in described membrane electrode assembly, polymer dielectric film is clipped between pair of electrodes, the side of membrane electrode assembly is provided with oxidant gas flow paths, and fuel gas flow path is provided with on the opposite side of membrane electrode assembly, fuel gas flow path and oxidant gas flow paths are arranged so that fuel gas and oxidant gas flow along contrary direction.The method of operation of described fuel cell comprises: in I) do not have moist condition or II) under the temperature of membrane electrode assembly is in the condition of at least 70 DEG C at least one condition, judge that whether the water yield near oxidant gas flow paths entrance is not enough; And if judge the water shortage near oxidant gas flow paths entrance, be then increased in the water yield near oxidant gas flow paths entrance by increase fuel gas flow and/or reduction fuel gas pressure.
By the method for operation of fuel cell with this structure, water near oxidant gas flow paths outlet has been transported near fuel gas flow path entrance by polymer dielectric film after, by the more water yield in fuel gas being transported near fuel gas flow path outlet, the more water yield can be transported near oxidant gas flow paths entrance by polymer dielectric film near fuel gas flow path outlet.Therefore, the water yield near oxidant gas flow paths entrance and the water yield near oxidant gas flow paths outlet can be regulated, trend towards in the prior art near described oxidant gas flow paths entrance becoming dry, trend towards in the prior art becoming wet near described oxidant gas flow paths outlet.As a result, anti-sealing when under not moist condition and/or under the condition of high temperature can be realized and be distributed in the operation on the surface of monocell unevenly.
The method of operation of above-mentioned fuel cell can also comprise: judge that whether the water yield near oxidant gas flow paths outlet is too much; If it is determined that the water shortage near oxidant gas flow paths entrance and/or the hypervolia near oxidant gas flow paths outlet, then by increasing fuel gas flow and/or reducing fuel gas pressure and promote that the water near oxidant gas flow paths outlet is transported near oxidant gas flow paths entrance via fuel gas flow path, thus the water yield be increased near oxidant gas flow paths entrance and the water yield reduced near oxidant gas flow paths outlet; In I) do not have moist condition or II) under the temperature of membrane electrode assembly is in the condition of at least 70 DEG C at least one condition, judge that whether the water yield near oxidant gas flow paths entrance is too much; Judge that whether the water yield near oxidant gas flow paths outlet is not enough; And, if it is determined that the water shortage near oxidant gas flow paths entrance and/or oxidant gas flow paths outlet, then reduce the water yield of being taken out of from described battery by oxidant gas by reducing oxidizer gas flow rate and/or increase oxidant gas pressure and increase the water yield that can be transported to described fuel gas flow path entrance side from described oxidant gas flow paths outlet side.
By the method for operation of fuel cell with this structure, water near oxidant gas flow paths outlet has been transported near fuel gas flow path entrance by polymer dielectric film after, by the more water yield in fuel gas being transported near fuel gas flow path outlet, the more water yield can be transported near oxidant gas flow paths entrance by polymer dielectric film near fuel gas flow path outlet.Therefore, the water yield near oxidant gas flow paths entrance and the water yield near oxidant gas flow paths outlet can be regulated, trend towards in the prior art near described oxidant gas flow paths entrance becoming dry, trend towards in the prior art becoming wet near described oxidant gas flow paths outlet.As a result, anti-sealing when under not moist condition and/or under the condition of high temperature can be realized and be distributed in the operation on the surface of monocell unevenly.And, by fuel cell system of the present invention, by suppress to be taken away by oxidant gas and be discharged into the water yield of the outside of fuel cell, water can be gathered near oxidant gas flow paths outlet.
And the method for operation of above-mentioned fuel cell can also comprise: the resistance value measuring whole fuel cell; And when 105% of the minimum value of the resistance measured in advance of the monocell at each temperature that resistance value exceedes in multiple temperature and/or heap, judge the water shortage near oxidant gas flow paths entrance and/or the water shortage near oxidant gas flow paths outlet.
The water shortage that the method for operation with the fuel cell of this structure can use the simple method of the resistance value measuring whole fuel cell to determine exactly near oxidant gas flow paths entrance and exit.
And the method for operation of above-mentioned fuel cell can also comprise: the voltage measuring whole fuel cell; And when 95% of the maximum of the voltage measured in advance of the monocell at each temperature that voltage is less than in multiple temperature and/or heap, judge the hypervolia near oxidant gas flow paths entrance and/or the hypervolia near oxidant gas flow paths outlet.
The hypervolia that the method for operation with the fuel cell of this structure can use the simple method of the voltage measuring whole fuel cell to determine exactly near oxidant gas flow paths entrance and exit.
And the method for operation of above-mentioned fuel cell can also comprise: measure the pressure drop flowing through the oxidant gas of oxidant gas flow paths; And when pressure drop is less than 105% of the minimum value of the pressure drop of measuring in advance of the oxidant gas flowing through oxidant gas flow paths, judge the water shortage near oxidant gas flow paths entrance and/or the water shortage near oxidant gas flow paths outlet.
The method of operation with the fuel cell of this structure can use the water shortage measured the simple method flowing through the pressure drop of the oxidant gas of oxidant gas flow paths and determine exactly near oxidant gas flow paths entrance and exit.
And the method for operation of above-mentioned fuel cell can also comprise: measure the pressure drop flowing through the oxidant gas of oxidant gas flow paths; And when pressure drop exceedes 105% of the maximum of the pressure drop of measuring in advance of the oxidant gas flowing through oxidant gas flow paths, judge the hypervolia near oxidant gas flow paths entrance and/or the hypervolia near oxidant gas flow paths outlet.
The method of operation with the fuel cell of this structure can use the hypervolia measured the simple method flowing through the pressure drop of the oxidant gas of oxidant gas flow paths and determine exactly near oxidant gas flow paths entrance and exit.
And in the method for operation of above-mentioned fuel cell, fuel gas pressure can be reduced to and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa.
Due to by fuel gas pressure being reduced to the enough water yields maintained in fuel gas in suitable scope, the water yield that the method for operation with the fuel cell of this structure can be increased in the water yield near oxidant gas flow paths entrance and reduce near oxidant gas flow paths outlet.
And in the method for operation of above-mentioned fuel cell, the stoichiometric proportion of oxidant gas can be reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0.
Due to by the stoichiometric proportion of oxidant gas is reduced to the water yield that in suitable scope, minimizing is taken out of from fuel cell by oxidant gas, the method for operation with the fuel cell of this structure can reduce the water yield near oxidant gas flow paths entrance and be increased in the water yield near oxidant gas flow paths outlet.
And in the method for operation of above-mentioned fuel cell, the stoichiometric proportion of fuel gas can increase to and is more than or equal to 1.0 and is less than or equal in the scope of 10.
The method of operation with the fuel cell of this structure can by increasing in suitable scope by the stoichiometric proportion of fuel gas, when not making polymer dielectric film become dry, the water yield being increased in the water yield near oxidant gas flow paths entrance and reducing near oxidant gas flow paths outlet.
And in the method for operation of above-mentioned fuel cell, oxidant gas pressure can increase to and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa.
Due to by oxidant gas pressure being increased to the water yield that in suitable scope, minimizing is taken out of from fuel cell by oxidant gas, the method for operation with the fuel cell of this structure can reduce the water yield near oxidant gas flow paths entrance and be increased in the water yield near oxidant gas flow paths outlet.
And, the method of operation of above-mentioned fuel cell can also comprise: if it is determined that the water shortage near oxidant gas flow paths entrance, then the stoichiometric proportion of fuel gas increases to and is more than or equal to 1.0 and is less than or equal in the scope of 10 by one or many, and/or is reduced to by fuel gas pressure and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa; Then, after judging the water shortage near oxidant gas flow paths outlet, stop controlling fuel gas; Then, the stoichiometric proportion of oxidant gas is reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0 by one or many, and/or is increased to by oxidant gas pressure and be more than or equal to atmospheric pressure and be less than or equal in the scope of 0.3MPa; Then, after judging the hypervolia near oxidant gas flow paths outlet, stop controlled oxidization agent gas; Then, if it is determined that the water shortage near oxidant gas flow paths entrance, then again start to control fuel gas, and if judge that the water yield near oxidant gas flow paths entrance is not not enough, then continue operation of fuel cells.
By the method for operation of fuel cell with this structure, when judging the water shortage near oxidant gas flow paths entrance, after promoting that by controlling fuel gas water is transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet, be increased in the water yield near oxidant gas flow paths outlet by controlled oxidization agent gas, both not many also not suitable water yields very little can be maintained near oxidant gas flow paths entrance and exit.And, by the method for operation of fuel cell of the present invention, can by making about the whether not enough final judgement of the water yield near oxidant gas flow paths entrance, and if water shortage, then by again repeating series of steps, prevent the water in whole oxidant gas flow paths from distributing unevenly.
And, the method of operation of above-mentioned fuel cell can also comprise: if it is determined that the water shortage near oxidant gas flow paths entrance, then the stoichiometric proportion of oxidant gas is reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0 by one or many, and/or is increased to by oxidant gas pressure and be more than or equal to atmospheric pressure and be less than or equal in the scope of 0.3MPa; Then, after judging the hypervolia near oxidant gas flow paths outlet, stop controlled oxidization agent gas; Then, the stoichiometric proportion of fuel gas increases to and is more than or equal to 1.0 and is less than or equal in the scope of 10 by one or many, and/or is reduced to by fuel gas pressure and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa; Then, after judging the water shortage near oxidant gas flow paths outlet, stop controlling fuel gas; Then, if it is determined that the water shortage near oxidant gas flow paths entrance, then again start controlled oxidization agent gas, and if judge that the water yield near oxidant gas flow paths entrance is not not enough, then continue operation of fuel cells.
By the method for operation of fuel cell with this structure, when judging the water shortage near oxidant gas flow paths entrance, suppressed water to be transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet by controlled oxidization agent gas, and assembled the water having q.s near oxidant gas flow paths outlet after, promote that by controlling fuel gas water is transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet, both not many also not suitable water yields very little can be maintained near oxidant gas flow paths entrance and exit.And, by the method for operation of fuel cell of the present invention, can by making about the whether not enough final judgement of the water yield near oxidant gas flow paths entrance, and if water shortage, then by again repeating series of steps, prevent the water in whole oxidant gas flow paths from distributing unevenly.
And, the method of operation of above-mentioned fuel cell can also comprise: the stoichiometric proportion of fuel gas increases to and is more than or equal to 1.0 and is less than or equal in the scope of 10 by one or many, and/or is reduced to by fuel gas pressure and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa; Then, after judging the water shortage near oxidant gas flow paths outlet, stop controlling fuel gas; Then, the stoichiometric proportion of oxidant gas is reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0 by one or many, and/or is increased to by oxidant gas pressure and be more than or equal to atmospheric pressure and be less than or equal in the scope of 0.3MPa; Then, after judging the hypervolia near oxidant gas flow paths outlet, stop controlled oxidization agent gas; Then, the stoichiometric proportion of fuel gas is increased to and is more than or equal to 1.0 and is less than or equal in the scope of 10, and/or fuel gas pressure is reduced to is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa; And then, if it is determined that the water shortage near oxidant gas flow paths outlet, then again start controlled oxidization agent gas, and if judge that the water yield near oxidant gas flow paths outlet is not not enough, then stop controlling fuel gas and continuing operation of fuel cells.
By the method for operation of fuel cell with this structure, by first making the water yield near oxidant gas flow paths outlet suitably not enough by controlling fuel gas, then suppressed water to be transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet by controlled oxidization agent gas, and assembled the water having q.s near oxidant gas flow paths outlet after, promote that by controlling fuel gas water is transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet, both not many also not suitable water yields very little can be maintained near oxidant gas flow paths entrance and exit.And, just the catalyst layer of its original performance can not be maintained (such as once become wet when operation has, this catalyst layer: the small aperture wherein in catalyst layer is got clogged by oxidation catalyst wittingly) fuel cell time, the method of operation of fuel cell of the present invention is especially effective, this is because this fuel cell can not allow catalyst layer become wet.
And, the method of operation of above-mentioned fuel cell can also comprise: the stoichiometric proportion of oxidant gas is reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0 by one or many, and/or is increased to by oxidant gas pressure and be more than or equal to atmospheric pressure and be less than or equal in the scope of 0.3MPa; Then, after judging the hypervolia near oxidant gas flow paths outlet, stop controlled oxidization agent gas; Then, the stoichiometric proportion of fuel gas increases to and is more than or equal to 1.0 and is less than or equal in the scope of 10 by one or many, and/or is reduced to by fuel gas pressure and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa; Then, after judging the water shortage near oxidant gas flow paths outlet, stop controlling fuel gas; Then, the stoichiometric proportion of oxidant gas is reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0, and/or oxidant gas pressure is increased to be more than or equal to atmospheric pressure and be less than or equal in the scope of 0.3MPa; And then, if it is determined that the hypervolia near oxidant gas flow paths outlet, then again start to control fuel gas, and if judge that the water yield is not too much, then stop controlled oxidization agent gas and continue operation of fuel cells.
By the method for operation of fuel cell with this structure, by first making the water yield near oxidant gas flow paths outlet suitably too much by controlled oxidization agent gas, then promote by controlling fuel gas that water is transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet, and the water yield be then increased in by controlled oxidization agent gas near oxidant gas flow paths outlet, can maintain both not many also not suitable water yields very little near oxidant gas flow paths entrance and exit.And, when operation have just can not maintain its original performance once become dry dielectric film (such as, cross carbon fluoro sulfonate dielectric film) fuel cell time, the method of operation of fuel cell of the present invention is especially effective, this is because this fuel cell can not allow dielectric film become dry.
According to the present invention, water near oxidant gas flow paths outlet has been transported near fuel gas flow path entrance by polymer dielectric film after, by the more water yield in fuel gas being transported near fuel gas flow path outlet, the more water yield can be transported near oxidant gas flow paths entrance by polymer dielectric film near fuel gas flow path outlet.Therefore, the water yield near oxidant gas flow paths entrance and the water yield near oxidant gas flow paths outlet can be regulated, trend towards in the prior art near described oxidant gas flow paths entrance becoming dry, trend towards in the prior art becoming wet near described oxidant gas flow paths outlet.As a result, when can work as under not moist condition and/or under the condition of high temperature, anti-sealing is distributed on the surface of monocell unevenly.And fuel cell system of the present invention has decision maker, so the water shortage near oxidant gas flow paths entrance can be determined exactly.
Accompanying drawing explanation
By in the detailed description of the exemplary embodiment of the present invention referring to accompanying drawing, feature of the present invention, advantage and technology and industrial significance are described, Reference numeral identical in the accompanying drawings represents identical element, wherein:
Fig. 1 is the cutaway view of the frame form of the monocell illustrated in fuel cell system of the present invention, and described frame form cuts along stacking direction;
Fig. 2 is the cutaway view of the frame form of the water circulation illustrated in the monocell of fuel cell system of the present invention;
Fig. 3 is the view of the frame form of the typical case that preferred fuel cell system is shown, this fuel cell system is for performing the method for operation of fuel cell of the present invention;
Fig. 4 is the flow chart of the program of the typical case that preferred fuel cell system is shown, this fuel cell system is for performing the method for operation of fuel cell of the present invention;
Fig. 5 is the flow chart of the program of the second typical case that preferred fuel cell system is shown, this fuel cell system is for performing the method for operation of fuel cell of the present invention;
Fig. 6 is the flow chart of the program of the 3rd typical case that preferred fuel cell system is shown, this fuel cell system is for performing the method for operation of fuel cell of the present invention;
Fig. 7 is the flow chart of the program of the 4th typical case that preferred fuel cell system is shown, this fuel cell system is for performing the method for operation of fuel cell of the present invention;
Fig. 8 is the flow chart of the program of the 5th typical case that preferred fuel cell system is shown, this fuel cell system is for performing the method for operation of fuel cell of the present invention;
Fig. 9 is the flow chart of the program of the 6th typical case that preferred fuel cell system is shown, this fuel cell system is for performing the method for operation of fuel cell of the present invention;
Figure 10 is the flow chart of the program of the 7th typical case that preferred fuel cell system is shown, this fuel cell system is for performing the method for operation of fuel cell of the present invention;
Figure 11 is the flow chart of the program of the 8th typical case that preferred fuel cell system is shown, this fuel cell system is for performing the method for operation of fuel cell of the present invention;
Figure 12 is the chart illustrating that cell voltage changes along with the change of the stoichiometric proportion of hydrogen;
Figure 13 is the chart illustrating that cell resistance changes along with the change of the stoichiometric proportion of hydrogen;
Figure 14 is the chart illustrating that the dewpoint humidity at anode export place changes along with the change of the stoichiometric proportion of hydrogen;
Figure 15 is the chart illustrating that the dewpoint humidity at cathode outlet place changes along with the change of the stoichiometric proportion of hydrogen;
Figure 16 is the chart illustrating that hydrogen pressure drop changes along with the change of the stoichiometric proportion of hydrogen; And
Figure 17 is the chart illustrating that air pressure changes along with the change of the stoichiometric proportion of hydrogen.
Embodiment
The method of operation of fuel cell of the present invention is a kind of method for operation of fuel cells, described fuel cell has heap, described heap comprises monocell, described monocell is provided with: I) membrane electrode assembly, in described membrane electrode assembly, solid polymer dielectric film is clipped between pair of electrodes, II) be arranged on oxidant gas flow paths on the side of membrane electrode assembly and III) be arranged on fuel gas flow path on the opposite side of membrane electrode assembly.Fuel gas flow path and oxidant gas flow paths are arranged so that fuel gas and oxidant gas flow along contrary direction.If in I) do not have moist condition or II) under the temperature of membrane electrode assembly is in the condition of at least 70 DEG C at least one condition, judge the water shortage near oxidant gas flow paths entrance, be then increased in the water yield near oxidant gas flow paths entrance by increase fuel gas flow and/or reduction fuel gas pressure.
A kind of fuel cell system comprising fuel cell for performing the of the present invention preferred fuel cell system of the method for operation of this fuel cell, described fuel cell has heap, described heap has monocell, described monocell has membrane electrode assembly, and in described membrane electrode assembly, solid polymer dielectric film is clipped between pair of electrodes.Fuel gas and oxidant gas are fed into fuel cell.Fuel cell system is in I) do not have moist condition or II) temperature of membrane electrode assembly operates under at least one condition in the condition of at least 70 DEG C.Fuel cell has fuel gas flow path on the side of membrane electrode assembly, and has oxidant gas flow paths on the opposite side of membrane electrode assembly.Fuel gas flow path and oxidant gas flow paths are arranged so that fuel gas and oxidant gas flow along contrary direction.In addition, fuel cell system is provided with: the decision maker judging the water yield near oxidant gas flow paths entrance; With fuel gas control device, if judge the water shortage near oxidant gas flow paths entrance in this decision maker, then described fuel gas control device is increased in the water yield near oxidant gas flow paths entrance by increasing fuel gas flow and/or reducing fuel gas pressure.
The method of operation of fuel cell of the present invention is a kind of method for operation of fuel cells, described fuel cell has heap, described heap comprises monocell, described monocell is provided with: I) membrane electrode assembly, in described membrane electrode assembly, solid polymer dielectric film is clipped between pair of electrodes, II) be arranged on oxidant gas flow paths on the side of membrane electrode assembly and III) be arranged on fuel gas flow path on the opposite side of membrane electrode assembly.Fuel gas flow path and oxidant gas flow paths are arranged so that fuel gas and oxidant gas flow along contrary direction.If in I) do not have moist condition, or II) under the temperature of membrane electrode assembly is in the condition of at least 70 DEG C at least one condition, judge the water shortage near oxidant gas flow paths entrance and/or the hypervolia near oxidant gas flow paths outlet, then by increasing fuel gas flow and/or reducing fuel gas pressure and promote that the water near oxidant gas flow paths outlet is transported near oxidant gas flow paths entrance via fuel gas flow path, thus the water yield be preferably increased near oxidant gas flow paths entrance and the water yield preferably reduced near oxidant gas flow paths outlet.And, if in I) do not have moist condition or II) under the temperature of membrane electrode assembly is in the condition of at least 70 DEG C at least one condition, judge the water shortage near oxidant gas flow paths entrance and/or near oxidant gas flow paths outlet, then preferably reduce by reducing oxidizer gas flow rate and/or increase oxidant gas pressure the water yield of being taken out of from battery by oxidant gas and preferably increase can be transported to the water yield of fuel gas flow path entrance side from oxidant gas flow paths outlet side.
A kind of fuel cell system comprising fuel cell for performing the of the present invention preferred fuel cell system of the method for operation of this fuel cell, described fuel cell has heap, described heap has monocell, described monocell has membrane electrode assembly, and in described membrane electrode assembly, solid polymer dielectric film is clipped between pair of electrodes.Fuel gas and oxidant gas are fed into fuel cell.Fuel cell system is in I) do not have moist condition or II) temperature of membrane electrode assembly operates under at least one condition in the condition of at least 70 DEG C.Fuel cell has fuel gas flow path on the side of membrane electrode assembly, and has oxidant gas flow paths on the opposite side of membrane electrode assembly.Fuel gas flow path and oxidant gas flow paths are arranged so that fuel gas and oxidant gas flow along contrary direction.In addition, fuel cell system is provided with: decision maker; And at least one in fuel gas control device or oxidant gas control device.Decision maker judges the water yield near oxidant gas flow paths entrance and/or near oxidant gas flow paths outlet.If judge the water shortage near oxidant gas flow paths entrance and/or the hypervolia near oxidant gas flow paths outlet in this decision maker, then fuel gas control device is by increasing fuel gas flow and/or reducing fuel gas pressure and promote that the water near oxidant gas flow paths outlet is transported near oxidant gas flow paths entrance via fuel gas flow path, thus the water yield be increased near oxidant gas flow paths entrance and the water yield reduced near oxidant gas flow paths outlet.If to judge in this decision maker near oxidant gas flow paths entrance and/or water shortage near oxidant gas flow paths outlet, then oxidant gas control device reduces the water yield of being taken out of from battery by oxidant gas and increases the water yield that can be transported to fuel gas flow path entrance side from oxidant gas flow paths outlet side by reducing oxidizer gas flow rate and/or increase oxidant gas pressure.
Here, solid polymer dielectric film is a kind of use solid polymer dielectric film in a fuel cell.Its example comprises: fluoropolymer dielectric film, and it comprises the fluoropolymer electrolyte crossing carbon fluoro sulfonate such as represented by NAFION (trade name); And hydrocarbon polymer dielectric film, it comprises hydrocarbon polymer electrolyte, in described hydrocarbon polymer electrolyte, such as the proton acidic group of sulfonic group, carboxylic acid group or phosphate is (namely, proton conduction base) be introduced in hydrocarbon polymer, this hydrocarbon polymer is such as engineering plastics or general-purpose plastics, and described engineering plastics are such as polyether-ether-ketone, polyether-ketone, polyether sulfone, polyphenylene sulfide, polyphenylethyl or poly-phenylene vinylene (ppv) (polyparaphenylene).
Each electrode has catalyst layer and gas diffusion layers.Catalyst layer can use the catalyst ink (catalystink) containing catalyst, conductive material and polymer dielectric to be formed.Catalyst is normally carried on the catalyst component in conductive particles.Catalyst component is especially unrestricted, as long as its oxidation reaction relative to the fuel at fuel electrode place or have catalytic property in the reduction reaction of the oxidant at oxidant electrode place.The catalyst component be usually used in polymer electrolyte fuel cells can be used.Such as, the metal of platinum or platinum alloy and such as ruthenium, iron, nickel, manganese, cobalt or copper can be used.
Conductive particles as catalyst carrier can be the material with carbon element of the conduction of carbon granule as carbon fiber or such as carbon black, or the metal material of such as metallic particles or metallic fiber.Conductive material is also for providing conductibility to catalyst layer.
Catalyst ink obtains by catalyst and all those polymer dielectrics being described above dissolved or dispersed in solvent.Polymer dielectric is a kind of use polymer dielectric in a fuel cell.Concrete example comprises: fluoropolymer electrolyte; Such as be used in those the hydrocarbon polymer electrolyte in above-mentioned solid polymer dielectric film.Can the solvent of suitably selecting catalyst ink.Such as, such as METHYLPYRROLIDONE (NMP) can be used, methyl-sulfoxide (DMSO), or the organic solvent of the such as alcohol of methyl alcohol, ethanol or propyl alcohol, or the mixture of these organic solvents, or the mixture of these organic solvents and water.Catalyst ink can also comprise other composition except catalyst and electrolyte if desired, and such as adhesive or water come off resin.
Can suitably select for applying the method with dry catalyst ink.Such as, the example of applying method comprises: spraying, silk screen printing, doctor blade method, intaglio printing and mouth die etc.And the example of drying means comprises: drying under reduced pressure, heat drying and heat drying under reduced pressure.Specified conditions for drying under reduced pressure and heat drying are unrestricted and can suitably set.The amount of the catalyst ink applied is according to different for the catalyst performance of the catalyst metals of electrode catalyst and the composition of catalyst ink, but the amount of the catalyst component of per unit area is about 0.01mg/cm 2to 2.0mg/cm 2enough.And the thickness of catalyst layer is especially unrestricted, and to be about 1 μm to 50 μm be enough.
The formation method of catalyst layer is not by specific restriction.Such as, catalyst layer can by the surface that catalyst ink is applied to gas diffusion layers sheet material makes it dry and is formed on the surface of gas diffusion layers sheet material.Or catalyst layer can by the surface that catalyst ink is applied to dielectric film makes it dry and is formed on the surface of dielectric film.Or, catalyst layer can be formed on the surface of dielectric film or gas diffusion sheet material as follows: first by the surface that catalyst ink is applied to translate substrate makes its drying, then to be combined by hot compression or this transfer sheet is spread sheet material with dielectric film or gas and is combined by similar method, and then peel off the substrate film of transfer sheet.
The gas diffusion layers sheet material forming gas diffusion layers has the gas diffusibility and the conductibility that enable gas effectively be supplied to catalyst layer, and has the strength of materials of the formation gas diffusion layers of requirement.Such as, gas diffusion layers sheet material can be formed by conducting porous body, described conducting porous style as: carbon porous body is such as carbon paper, cross shaped head carbon fiber (carboncross) or carbon felt; Or metal porous body or metal grill, it is formed by the metal of such as titanium, aluminium, copper, nickel, nichrome, copper alloy, silver, aluminium alloy, kirsite, lead alloy, niobium, tantalum, iron, stainless steel, gold or platinum.The thickness of conducting porous body is preferably about 50 μm to 500 μm.
Gas diffusion layers can be formed by the conducting porous body of individual layer as above, but water stratum disjunction also can be arranged on the side of catalyst layer.Water stratum disjunction has loose structure usually, the conductive particles of resin and analog and such as carbon granule and carbon fiber and the water comprising such as polytetrafluoroethylene (PTFE) comes off.Water stratum disjunction is always unrequired, but the favourable part of water stratum disjunction is, when water stratum disjunction keeps the water yield in catalyst layer and dielectric film fully, water stratum disjunction, except improving the hydrophobicity of gas diffusion layers, can also improve the electrical contact between catalyst layer and gas diffusion layers.
The membrane electrode assembly manufactured clamps to form monocell by spacer then.Spacer has the character of conductive properties and air seal, and can play the function of gatherer and seals.Such as, can use: carbon spacer, it has high carbon fiber content and is formed by the synthetic with resin; Or metal spacer, it uses metal material.The example of metal spacer comprises: the metal spacer be made up of highly corrosion resistant metal material; With its surface with carbon or highly corrosion resistant metal material or analog coated with the metal spacer increasing corrosion resistance.Be formed with the flow path for supplying fuel gas and oxidant gas in the spacer.
Be used in the gas in the positive electrode of typical fuel cell, be more specifically, hydrogen, the fuel gas in the method for operation of fuel cell system of the present invention or fuel cell can be used as.Be used in the gas in the negative electrode of typical fuel cell, be more specifically, oxygen, the oxidant gas in the method for operation of fuel cell system of the present invention or fuel cell can be used as.
Fig. 1 is the cutaway view of the frame form of the example that above-mentioned monocell is shown, described frame form cuts along stacking direction.As shown in the drawing, the monocell 100 of the fuel cell in fuel cell system of the present invention has membrane electrode assembly 8, and in described membrane electrode assembly 8, polymer dielectric film 1 is clipped between negative electrode 6 and positive electrode 7.Monocell 100 also has a pair sept 9 and 10, and described a pair sept 9 and 10 is from the outside clamping membrane electrode assembly 8 of electrode.Negative electrode 6 side guarantees there is oxidant gas flow paths 11 at the boundary of sept and electrode, and guarantee there is fuel gas flow path 12 at the boundary of sept and electrode on positive electrode 7 side.Negative electrode is formed by the cathode catalyst layer 2 be stacked and gas diffusion layers 4.Positive electrode 7 is formed by the anode catalyst layer 3 be stacked and gas diffusion layers 5.In addition, oxidant gas flow paths 11 and fuel gas flow path 12 are arranged so that fuel gas and oxidant gas flow along contrary direction.Here, in flow path 11 and 12 in FIG, the symbol of the circle that center has a little represents, gas flows along the direction vertical with the paper it being drawn drawings attached, and towards the direction of the people seen to accompanying drawing.The symbol that center has the circle of X represents, gas flows along the direction vertical with the paper it being drawn drawings attached, and away from the direction of the people seen to accompanying drawing.In addition, although do not illustrate particularly, but the region near the entrance of oxidant gas flow paths 11 is on the side relative with the region near the outlet of fuel gas flow path 12 of dielectric film 1, and the region near the outlet of oxidant gas flow paths 11 is on the side relative with the region near the entrance of fuel gas flow path 12 of dielectric film 1.Incidentally, in FIG, gas flow paths is all plotted as the flow path of S shape, but gas flow paths is not any specific shape.That is, they can be any shapes, as long as fuel gas and oxidant gas flow along contrary direction.
For judging that the example of the method for the water yield near oxidant gas flow paths entrance and exit can be, measure the resistance value of whole fuel cell, and when the minimum value of the resistance measured in advance of at least one in the monocell at each temperature that this resistance value is equal to or greater than in multiple temperature or heap, judge that the inner side of monocell or heap is dry.For for judging that the reason of the position of the water yield near oxidant gas flow paths entrance is, because be arranged in the fuel cell in vehicle, such as, typically, air is used as oxidant gas, and hydrogen be used as fuel gas, and the gas flow under given stoichiometric proportion be air more than hydrogen, make it possible to supposition monocell or heap will first start in oxidant gas flow paths porch become dry.For for judge the position of the water yield oxidant gas flow paths outlet near reason be, because think at operation fuel gas control device (such as, the fuel gas control device will illustrated below) after, the water yield near oxidant gas flow paths outlet can be interim not enough.
Decision maker can be configured to the resistance value measuring whole fuel cell, and when 105% of the minimum value of the resistance measured in advance of at least one in the monocell at each temperature that resistance value exceedes in multiple temperature or heap, judge I) whether the water yield near oxidant gas flow paths entrance is not enough, and/or II) water yield whether not enough (decision maker A will be called below this decision maker) near oxidant gas flow paths outlet.This is because, by measuring the simple method of the resistance value of whole fuel cell, the water shortage near oxidant gas flow paths entrance and exit can be determined exactly.Incidentally, more preferably, when 110% of the minimum value of the resistance measured in advance of at least one in the monocell at each temperature that the resistance value of whole fuel cell exceedes in multiple temperature or heap, judge water shortage, and even more preferably, when 120% of the minimum value of the resistance measured in advance of at least one in the monocell at each temperature that the resistance value of whole fuel cell exceedes in multiple temperature or heap, judge water shortage.
And, for judging that an example of the method for the water yield near oxidant gas flow paths entrance and exit is, measure the pressure drop flowing through the oxidant gas of oxidant gas flow paths, and when pressure drop is equal to or less than the pressure drop of measuring in advance of the oxidant gas flowing through oxidant gas flow paths, judge that the inner side of monocell or heap is dry.
Decision maker can be configured to the pressure drop of measuring the oxidant gas flowing through oxidant gas flow paths, and when pressure drop is less than 105% of the minimum value of the pressure drop of measuring in advance of the oxidant gas flowing through oxidant gas flow paths, judge I) whether the water yield near oxidant gas flow paths entrance is not enough, and/or II) water yield whether not enough (decision maker C will be called below this decision maker) near oxidant gas flow paths outlet.This is because, by measuring the simple method flowing through the pressure drop of the oxidant gas of oxidant gas flow paths, the water shortage near oxidant gas flow paths entrance and exit can be determined exactly.Incidentally, more preferably, when the pressure drop of the oxidant gas flowing through oxidant gas flow paths is less than 100% of the minimum value of the pressure drop of measuring in advance of the oxidant gas flowing through oxidant gas flow paths, judge water shortage, and even more preferably, when the pressure drop of the oxidant gas flowing through oxidant gas flow paths is less than 95% of the minimum value of the pressure drop of measuring in advance of the oxidant gas flowing through oxidant gas flow paths, judge water shortage.
And, for measuring an example of the method for the water yield near oxidant gas flow paths entrance and exit be, measure the voltage of whole fuel cell, and when the maximum of the voltage measured in advance of at least one in the monocell at each temperature that voltage is equal to or less than in multiple temperature or heap, judge there is too much water in monocell or in heap.
Decision maker can be configured to the voltage measuring whole fuel cell, and when 95% of the maximum of the voltage measured in advance of at least one in the monocell at each temperature that voltage is less than in multiple temperature or heap, judge I) whether the water yield near oxidant gas flow paths entrance is too much, and/or II) too much (will be called decision maker B below this decision maker) whether the water yield near oxidant gas flow paths outlet.This is because, by measuring the simple method of the voltage of whole fuel cell, the hypervolia near oxidant gas flow paths entrance and exit can be determined exactly.Incidentally, more preferably, when 90% of the minimum value of the voltage measured in advance of at least one in the monocell at each temperature that the voltage of whole fuel cell is less than in multiple temperature or heap, judge hypervolia, and even more preferably, when 85% of the minimum value of the voltage measured in advance of at least one in the monocell at each temperature that the voltage of whole fuel cell is less than in multiple temperature or heap, judge hypervolia.
And, measure to flow through the pressure drop of the oxidant gas of oxidant gas flow paths for measuring an example of the method for the water yield near oxidant gas flow paths entrance and exit, and when pressure drop is equal to or greater than the pressure drop of measuring in advance of the oxidant gas flowing through oxidant gas flow paths, judge there is too much water in monocell or in heap.
Decision maker can be configured to the pressure drop of measuring the oxidant gas flowing through oxidant gas flow paths, and when pressure drop exceedes 105% of the maximum of the pressure drop of measuring in advance of the oxidant gas flowing through oxidant gas flow paths, whether too much (below this decision maker, decision maker D will be called) to judge the water yield near the oxidant gas flow paths entrance water yield whether too much and/or near oxidant gas flow paths outlet.This is because, by measuring the simple method flowing through the pressure drop of the oxidant gas of oxidant gas flow paths, the hypervolia near oxidant gas flow paths entrance and exit can be determined exactly.Incidentally, more preferably, when the pressure drop of the oxidant gas flowing through oxidant gas flow paths exceedes 110% of the maximum of the pressure drop of measuring in advance of the oxidant gas flowing through oxidant gas flow paths, judge hypervolia, and even more preferably, when the pressure drop of the oxidant gas flowing through oxidant gas flow paths exceedes 120% of the maximum of the pressure drop of measuring in advance of the oxidant gas flowing through oxidant gas flow paths, judge hypervolia.
If judge the water shortage near oxidant gas flow paths entrance and/or the hypervolia near oxidant gas flow paths outlet by above-mentioned decision maker or another kind of method, then the method for operation of fuel cell system of the present invention or fuel cell is by increasing fuel gas flow and/or reducing the water yield that fuel gas pressure is increased in the water yield near oxidant gas flow paths entrance and reduces near oxidant gas flow paths exports.And, if judge the water shortage near oxidant gas flow paths entrance and/or near oxidant gas flow paths outlet by above-mentioned decision maker or another kind of method, then the method for operation of fuel cell system of the present invention or fuel cell reduces the water yield of being taken out of from battery by oxidant gas by reducing oxidizer gas flow rate and/or increasing oxidant gas pressure and increases the water yield that can be transported to fuel gas flow path entrance side from oxidant gas flow paths outlet side.
Incidentally, the amount of the steam in the gas flowing through gas flow paths, the gas flow of non-humidification, the dividing potential drop of steam and comprise steam gas total pressure between set up the relation shown in expression formula (3) such as, this pass be fuel gas flow path and oxidant gas flow paths share.
Q H 2 O = Q d r y × P H 2 O P t o t a l - P H 2 O - - - ( 3 )
(wherein, Q h2Orepresent the amount of the steam in gas, Q dryrepresent the flow of the gas of non-humidification, P h2Orepresent the dividing potential drop of steam, and P totalrepresent the total pressure comprising the gas of steam.)
From expression formula (3), Q h2Owith Q dryproportional, so be apparent that, the flow Q of the gas of non-humidification to be supplied dryneed remain on a certain flow place or remain on more than a certain flow, to make the amount Q of the steam in gas h2Oremain on some amount places or remain on more than some amounts.But, as indicated by the power generation performance of the change of the amount by the fuel gas along with supply and the dewpoint humidity at cathode outlet place (will illustrate below), if the flow of fuel gas increases too much, then polymer dielectric film will become dry near oxidant gas flow paths entrance, and this will cause decrease of power generation.That is, in fact in order to maintain good generating efficiency, the flow Q of the gas of non-humidification drymust increase in suitable scope.And from expression formula (3), be apparent that, comprising the total pressure P of gas of steam totalwith the dividing potential drop P of steam h2Obetween difference (that is, P total-P h2O), that is, the dividing potential drop of the gas of non-humidification to be supplied, with the amount Q of the steam in gas h2Obe inversely proportional to.Therefore, along with the dividing potential drop of the gas of non-humidification is suppressed, Q h2Ocan increase.But, if the dividing potential drop of the gas of non-humidification is suppressed too much, then takes away too many water by near oxidant gas flow paths entrance, cause the polymer dielectric film near oxidant gas flow paths entrance to become too dry.Therefore, in fact in order to maintain good generating efficiency, dividing potential drop (that is, the P of the gas of non-humidification total-P h2O) must be reduced in suitable scope.Therefore, in order to obtain effect of the present invention, for the flow Q of the gas of non-humidification drythere is higher limit, and dividing potential drop (that is, the P of gas for non-humidification total-P h2O) there is lower limit.As a result, in fact " continue to increase Q by means of only execution dry" or " continue to reduce dividing potential drop (P total-P h2O) " simple operations, Q h2Omore than some amount places or some amounts can not be maintained.But, by being adjusted within the scope of some by these two values, good generating efficiency can be maintained.
Operation about the amount of steam also can be applied to oxidant gas and control.From expression formula (3), Q h2Owith Q dryproportional, so be apparent that, the flow Q of the gas of non-humidification to be supplied dryneed remain on a certain flow place or remain on below a certain flow, to make the amount Q of the steam in gas h2Oremain on some amount places or remain on below some amounts.But if the flow of oxidant gas reduces too much, then the water taken out of from fuel cell by oxidant gas will reduce.As a result, near oxidant gas flow paths outlet, so-called water logging will occur, this will cause decrease of power generation.That is, in fact in order to maintain good generating efficiency, the flow Q of the gas of non-humidification drymust be reduced in suitable scope.And, from expression formula (3), be apparent that, comprising the total pressure P of gas of steam totalwith the dividing potential drop P of steam h2Obetween difference (that is, P total-P h2O), that is, the dividing potential drop of the gas of non-humidification to be supplied, with the amount Q of the steam in gas h2Obe inversely proportional to.Therefore, along with the dividing potential drop of the gas of non-humidification increases, Q h2Ocan be suppressed.But, if the dividing potential drop of the gas of non-humidification is suppressed too much, then will take away inadequate water near oxidant gas flow paths entrance, and also cause, near oxidant gas flow paths outlet, water logging occurs.Therefore, in fact in order to maintain good generating efficiency, dividing potential drop (that is, the P of the gas of non-humidification total-P h2O) must be increased in suitable scope.Therefore, in order to obtain effect of the present invention, for the flow Q of the gas of non-humidification drythere is lower limit, and dividing potential drop (that is, the P of gas for non-humidification total-P h2O) there is higher limit.As a result, in fact " continue to reduce Q by means of only execution dry" or " continue to increase dividing potential drop (P total-P h2O) " simple operations, good generating efficiency can not be maintained.But, by being adjusted within the scope of some by these two values, good generating efficiency can be maintained.
Fig. 2 is the cutaway view of the frame form of the water circulation illustrated in the monocell of fuel cell system of the present invention.In order to illustrate, show negative electrode and positive electrode when not distinguishing gas diffusion layers and catalyst layer.Incidentally, center has the flow direction that symbol that the symbol of circle a little and center have a circle of X represents the gas flowing through flow path, as shown in Figure 1.And oxidant gas is drawn from oxidant gas flow paths entrance 11a and is flowed to oxidant gas flow paths outlet 11b, and fuel gas is drawn from fuel gas flow path entrance 12a and flowed to fuel gas flow path outlet 12b.Now, the region near oxidant gas flow paths outlet 11b becomes wet due to the water produced by the reaction shown in above expression formula (2).This water is brought near fuel gas flow path entrance 12a by polymer dielectric film 1, as shown in arrow 21.Now, the water be more brought near fuel gas flow path entrance 12a can by regulating the flow Q of the fuel gas of non-humidification as above dryand/or the dividing potential drop (P of the fuel gas of non-humidification total-P h2O) and be brought near fuel gas flow path outlet 12b.This water is brought near oxidant gas flow paths entrance 11a by polymer dielectric film 1, as shown in arrow 22, the water yield trending towards becoming dry near oxidant gas flow paths entrance 11a and trending towards near oxidant gas flow paths outlet 11b can be regulated thus to become the wet water yield.As a result, can realize a kind of not having moist while water be not distributed in the monocell on surface unevenly.
In addition, when the water yield near oxidant gas flow paths outlet 11b becomes dry, the water yield of being taken out of from fuel cell by oxidant gas can be reduced, thus by regulating the flow Q of the oxidant gas of non-humidification as above dryand/or the dividing potential drop (P of the oxidant gas of non-humidification total-P h2O) and water can be gathered near oxidant gas flow paths outlet 11b.
In order to maintain good generating efficiency, the stoichiometric proportion of fuel gas preferably increases to and is more than or equal to 1.0 and is less than or equal in the scope of 10.This is because, if stoichiometric proportion is more than 10, then polymer dielectric film becomes dry in fuel gas flow path porch, this causes decrease of power generation, and if stoichiometric proportion is less than 1.0, then can not supplies and operate necessary minimum gas flow under specific output, and, enough water yields can not be kept, because which limit the water yield that can be brought to oxidant gas flow paths by dielectric film in fuel gas.Especially, when fuel cell system of the present invention, fuel gas flow increases preferably by fuel metering gas supply device (will be called below this control device " fuel gas volume control device ").This is because fuel gas flow can be increased by the simple operations of fuel metering gas supply device.The example of fuel gas feeding device in this case comprises fuel gas tank and fuel gas pump.Incidentally, stoichiometric proportion more preferably increases to and is more than or equal to 1.0 and is less than or equal in the scope of 5.0, and most preferably increases to and be more than or equal to 1.0 and be less than or equal in the scope of 3.0.
In order to maintain good generating efficiency, fuel gas pressure is preferably reduced to and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa.This is because, if pressure is more than 0.3MPa, then can not keep enough water yields in fuel gas, and result, limit the water yield that can be brought to oxidant gas flow paths by dielectric film.And, if pressure is less than atmospheric pressure, then sufficiently can not supply the necessary fuel of generating.Especially, by fuel cell system of the present invention, fuel gas pressure reduces preferably by adjustment is arranged on the fuel gas pressure adjuster valve (will be called below this control device " fuel gas pressure control device ") near fuel gas flow path outlet.This is because fuel gas pressure can be reduced by the simple operations of fuel metering gas pressure adjuster valve.Fuel gas pressure is more preferably reduced to and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.2MPa, and is most preferably reduced to and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.1MPa.
Incidentally, also can by regulating fuel gas feeding device fuel metering gas pressure as above.But, only use fuel gas feeding device to be difficult to increase fuel gas flow simultaneously and reduce fuel gas pressure.Therefore, regulate fuel gas feeding device in fuel gas flow path porch in combination with the fuel gas pressure adjuster valve near exporting in fuel gas flow path, thus fuel gas flow can be increased and can fuel gas pressure be reduced.
In order to maintain good generating efficiency, the stoichiometric proportion of oxidant gas is preferably reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0.This is because, if stoichiometric proportion is more than 3.0, then can not keep enough water yields in oxidant gas flow paths, and result, limit the water yield that can be brought to fuel gas flow path by dielectric film, and if stoichiometric proportion is less than 1.0, then can not supplies and operate necessary minimum gas flow under specific output, and, the water logging in oxidant gas flow paths can not be avoided.Especially, by fuel cell system of the present invention, oxidizer gas flow rate reduces preferably by adjustment oxidant gas feedway (will be called below this control device " oxidizer gas flow rate control device ").This is because oxidizer gas flow rate can reduce by regulating the simple operations of oxidant gas feedway.The example of oxidant gas feedway in this case comprises oxidant gas tank and oxidizer gas pump.Incidentally, stoichiometric proportion is more preferably reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 2.5, and is most preferably reduced to and is more than or equal to 1.2 and is less than or equal in the scope of 2.0.
In order to maintain good generating efficiency, oxidant gas pressure preferably increases to and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa.This is because, if pressure is more than 0.3MPa, then can not avoid the water logging in oxidant gas flow paths.And, if pressure is less than atmospheric pressure, then can not keep enough water yields in oxidant gas flow paths, and result, limit the water yield that can be brought to fuel gas flow path by dielectric film.Especially, by fuel cell system of the present invention, oxidant gas pressure increases preferably by adjustment is arranged on the oxidant gas pressure adjuster valve (will be called below this control device " oxidant gas pressure control device ") near oxidant gas flow paths outlet.This is because oxidant gas pressure can increase by regulating the simple operations of oxidant gas pressure adjuster valve.Oxidant gas pressure more preferably increases to and is more than or equal to 0.12MPa and is less than or equal in the scope of 0.25MPa, and most preferably increases to and be more than or equal to 0.14MPa and be less than or equal in the scope of 0.2MPa.
Incidentally, also oxidant gas pressure can be regulated by regulating oxidant gas feedway as above.But, only use oxidant gas feedway to be difficult to reduce oxidizer gas flow rate simultaneously and increase oxidant gas pressure.Therefore, regulate oxidant gas feedway in oxidant gas flow paths porch in combination with the adjustment of oxidant gas pressure adjuster valve near exporting in oxidant gas flow paths, thus can oxidizer gas flow rate be reduced and can oxidant gas pressure be increased.
Fig. 3 is the view of the frame form of the typical case that preferred fuel cell system is shown, this fuel cell system is for performing the method for operation of fuel cell of the present invention.Incidentally, the fuel cell herein illustrated uses hydrogen as fuel gas, and uses air as oxidant gas.As shown in the drawing, fuel gas flow path and oxidant gas flow paths are arranged so that hydrogen (that is, fuel gas) and air (that is, oxidant gas) flow along contrary direction.And by hydrogen gas tank 31 and hydrogen pump 33 fuel metering gas flow (that is, fuel gas flow control), described hydrogen pump 33 is fuel gas feeding devices of a type.Incidentally, the hydrogen pump 33 in accompanying drawing is designed to reuse the hydrogen be not also consumed in fuel cell pack 200.In addition, Hydrogen Vapor Pressure (that is, fuel gas pressure controls) is regulated by hydrogen pressure regulating valve 34.More specifically, the structure of such system can make fuel gas flow increase and fuel gas pressure can be made to reduce.In addition, regulate oxidizer gas flow rate by air compressor (ACP) 44, described air compressor (ACP) is the oxidant gas feedway of a type.And, regulate air pressure by sort of air pressure adjusting valve 43.More specifically, the structure of such system can make oxidizer gas flow rate reduce and oxidant gas pressure can be made to increase.
And, as shown in Figure 3, gas flow surveying instrument is provided with (namely in fuel gas flow path and oxidant gas flow paths, hydrogen gas side has hydrogen gas tank 31 and there is the adjuster 32 of flowmeter 45 in air side) and gas pressure measurement device (that is, hydrogen gas side pressure gauge 35 and air side pressure table 42).
In addition, although do not illustrate in Fig. 3, in oxidant gas flow paths and fuel gas flow path, heap drop measurement device is provided with.More specifically, piling drop measurement device is be arranged on the porch of both oxidant gas flow paths and fuel gas flow path and the pressure sensor in exit.Pressure drop calculates as follows: Δ P (pressure drop)=P (inlet pressure)-P (outlet pressure).
And as shown in Figure 3, be provided with coolant temperature measurement mechanism 38 in the cooling system with radiator 36, to determine the state of fuel cell by deducing coolant temperature in advance, more specifically, fuel cell is dry or wet.Incidentally, preferably will be appointed as preset value to fixed temperature in the scope of 120 DEG C being more than or equal to 70 DEG C and being less than or equal to, and the value exceeding this set point is taken as the instruction for the exception (such as, uneven water distribution) in fuel cell.
In addition, as shown in Figure 3, the electrical system comprising voltmeter 40 and ammeter 39 also comprises power control unit (PCU) 41, for control overhead and for the voltage measured in advance that controls monocell 100 at each temperature in multiple temperature and/or heap 200 and resistance.
And, as shown in Figure 3, although fuel gas flow path also can be the non-regulated system of the terminal system of such as wherein discharging a small amount of fuel gas constantly, fuel gas flow path supposition has the regulatory function produced by hydrogen pump 33 and hydrogen pressure regulating valve 34.
Fig. 4 is the flow chart of the program of the typical case that preferred fuel cell system is shown, for the method for operation performing fuel cell of the present invention.Now, will suppose that wherein fuel cell system is the situation (S1) operated constantly under high loads.During operation, adopt a kind of mode judging the water yield, that is, measure the resistance value (S2) of whole fuel cell.Here, the minimum value of the monocell under next whether the step of execution being greater than in multiple temperature each temperature according to resistance value R and/or the resistance measured in advance of heap 105% value (hereinafter referred to as set point R 1) and different (that is, decision maker A).If resistance value R is equal to or less than R 1, then ongoing operation (S1) is under high loads proceeded.On the other hand, if resistance value R is greater than set point R 1, then judge the water shortage near oxidant gas flow paths entrance and/or near oxidant gas flow paths outlet, and fuel gas control device and/or oxidant gas control device operation (S3).Incidentally, although these two control device can also side by side operate (S3), but the usually fuel gas control device operation when water shortage near oxidant gas flow paths entrance, and oxidant gas control device operates when water shortage near exporting in oxidant gas flow paths.Fuel gas control device and oxidant gas control device can also regulate stoichiometric proportion and/or regulate pressure, but most preferably they regulate stoichiometric proportion simultaneously and regulate pressure.After fuel gas control device and/or oxidant gas control device operation (S3), measure the resistance value (S4) of whole fuel cell.If resistance value R is greater than set point R 1, then fuel gas control device and/or oxidant gas control device operate (S3) again.On the other hand, if resistance value R is equal to or less than set point R 1, then ongoing operation (S5) is under high loads proceeded.
Fig. 5 is the flow chart of the program of the second typical case that preferred fuel cell system is shown, for the method for operation performing fuel cell of the present invention.Now, will suppose that wherein fuel cell system is the situation (S11) operated constantly under high loads.During operation, adopt a kind of mode judging the water yield, that is, every voltage (S12) measuring whole fuel cell for 10 seconds to 10 minutes.Here, the maximum of the monocell under next whether the step of execution being less than in multiple temperature each temperature according to voltage E and/or the voltage measured in advance of heap 95% value (hereinafter referred to as set point E 1) and different (that is, decision maker B).If voltage E is equal to or greater than E 1, then ongoing operation (S11) is under high loads proceeded.On the other hand, if voltage E is less than set point E 1, then judge the hypervolia near oxidant gas flow paths entrance and/or near oxidant gas flow paths outlet, and fuel gas control device and/or oxidant gas control device operation (S13).Incidentally, although these two control device can also side by side operate (S13), but the usually oxidant gas control device operation when hypervolia near oxidant gas flow paths entrance, and fuel gas control device operates when hypervolia near exporting in oxidant gas flow paths.Fuel gas control device and oxidant gas control device can also regulate stoichiometric proportion and/or regulate pressure, but most preferably they regulate stoichiometric proportion simultaneously and regulate pressure.After fuel gas control device and/or oxidant gas control device operation (S13), measure the voltage (S14) of whole fuel cell.If voltage E is less than set point E 1, then fuel gas control device and/or oxidant gas control device operate (S13) again.On the other hand, if voltage E is equal to or greater than set point E 1, then ongoing operation (S15) is under high loads proceeded.
Fig. 6 is the flow chart of the program of the 3rd typical case that preferred fuel cell system is shown, for the method for operation performing fuel cell of the present invention.Now, will suppose that wherein fuel cell system is the situation (S21) operated constantly under high loads.During operation, adopt a kind of mode judging the water yield, that is, within every 10 seconds to 10 minutes, measure the pressure drop (S22) flowing through the oxidant gas of oxidant gas flow paths.Here, next whether the step of execution is less than the value of 105% of the minimum value of the pressure drop of measuring in advance of the oxidant gas flowing through oxidant gas flow paths (hereinafter referred to as set point Δ P according to pressure drop Δ P 1) and different (that is, decision maker C).If pressure drop Δ P is equal to or greater than Δ P 1, then ongoing operation (S21) is under high loads proceeded.On the other hand, if pressure drop Δ P is less than set point Δ P 1, then judge the water shortage near oxidant gas flow paths entrance and/or near oxidant gas flow paths outlet, and fuel gas control device and/or oxidant gas control device operation (S23).Incidentally, although these two control device can also side by side operate (S23), but the usually fuel gas control device operation when water shortage near oxidant gas flow paths entrance, and oxidant gas control device operates when water shortage near exporting in oxidant gas flow paths.Fuel gas control device and oxidant gas control device can also regulate stoichiometric proportion and/or regulate pressure, but most preferably they regulate stoichiometric proportion simultaneously and regulate pressure.After fuel gas control device and/or oxidant gas control device operation (S23), measure the pressure drop (S24) flowing through the oxidant gas of oxidant gas flow paths.If pressure drop Δ P is less than set point Δ P 1, then fuel gas control device and/or oxidant gas control device operate (S23) again.On the other hand, if pressure drop Δ P is equal to or greater than set point Δ P 1, then ongoing operation (S25) is under high loads proceeded.
Fig. 7 is the flow chart of the program of the 4th typical case that preferred fuel cell system is shown, for the method for operation performing fuel cell of the present invention.Now, will suppose that wherein fuel cell system is the situation (S31) operated constantly under high loads.During operation, adopt a kind of mode judging the water yield, that is, within every 10 seconds to 10 minutes, measure the pressure drop (S32) flowing through the oxidant gas of oxidant gas flow paths.Here, next whether the step of execution is greater than the value of 105% of the maximum of the pressure drop of measuring in advance of the oxidant gas flowing through oxidant gas flow paths (hereinafter referred to as set point Δ P according to pressure drop Δ P 2; Incidentally, Δ P 2with above-mentioned Δ P 1irrelevant) and different (that is, decision maker D).If pressure drop Δ P is equal to or less than Δ P 2, then ongoing operation (S31) is under high loads proceeded.On the other hand, if pressure drop Δ P is greater than set point Δ P 2, then judge the hypervolia near oxidant gas flow paths entrance and/or near oxidant gas flow paths outlet, and fuel gas control device and/or oxidant gas control device operation (S33).Incidentally, although these two control device can also side by side operate (S33), but the usually oxidant gas control device operation when hypervolia near oxidant gas flow paths entrance, and fuel gas control device operates when hypervolia near exporting in oxidant gas flow paths.Fuel gas control device and oxidant gas control device can also regulate stoichiometric proportion and/or regulate pressure, but most preferably they regulate stoichiometric proportion simultaneously and regulate pressure.After fuel gas control device and/or oxidant gas control device operation (S33), measure the pressure drop (S34) flowing through the oxidant gas of oxidant gas flow paths.If pressure drop Δ P is greater than set point Δ P 2, then fuel gas control device and/or oxidant gas control device operate (S33) again.On the other hand, if pressure drop Δ P is equal to or less than set point Δ P 2, then ongoing operation (S35) is under high loads proceeded.
A kind of pattern of fuel cell system of the present invention comprises: I) fuel gas control device; II) oxidant gas control device; III) decision maker A and/or decision maker C; IV) decision maker B and/or decision maker D; V) water conveying promotion control starting device A; VI) water conveying promotion control arresting stop A; VII) water conveying inhibitory control starting device A; VIII) water conveying inhibitory control arresting stop A; And IV) the final decision maker A of the not enough water yield.After judging the water shortage near oxidant gas flow paths entrance by decision maker A and/or C, water conveying promotes that controlling starting device A operates fuel gas control device one or many.After water conveying promotes that controlling starting device A operates fuel gas control device, after judged the water shortage near oxidant gas flow paths outlet by decision maker A and/or C, water conveying promotes that controlling arresting stop A stops fuel gas control device.After water conveying promotes that controlling arresting stop A stops fuel gas control device, water conveying inhibitory control starting device A operating oxidizer gas control equipment one or many.After judged the hypervolia near oxidant gas flow paths outlet by decision maker B and/or D, water conveying inhibitory control arresting stop A stops all elements of oxidant gas control device.After water conveying inhibitory control arresting stop A stops all elements of oxidant gas control device, if judge the water shortage near oxidant gas flow paths entrance by decision maker A and/or C, then the final decision maker A of the not enough water yield makes water carry promotion to control starting device A and again operates fuel gas control device, and if judge that the water yield near oxidant gas flow paths entrance is not not enough by decision maker A and/or C, then the final decision maker A of the not enough water yield continues operation of fuel cells.
Fig. 8 is the flow chart of the program of the 5th typical case that preferred fuel cell system is shown, for the method for operation performing fuel cell of the present invention.Now, will suppose that wherein fuel cell system is the situation (S41) operated constantly under high loads.During operation, within every 10 seconds to 10 minutes, coolant temperature T (S42) is measured by above-mentioned coolant temperature measurement mechanism.Now, if the coolant temperature T measured is equal to or less than set point T 1, then continuation (S41) is operated.On the other hand, if coolant temperature T is greater than set point T 1, then decision maker A operates (that is, measuring resistance) (S43).Now, if resistance value R is equal to or less than set point R 1, then judge to maintain the suitable water yield near oxidant gas flow paths entrance, therefore operation under high loads continues (S41).Incidentally, operation sequence is up to this point inherently identical with the Part I of the typical case shown in Fig. 4.Difference between this example and the typical case shown in Fig. 4 is, if resistance value R is greater than set point R 1, then the water yield near oxidant gas flow paths entrance increases as described below.
If resistance value R is greater than set point R 1then decision maker A (S43) judges the water shortage near oxidant gas flow paths entrance, and fuel gas volume control device and/or fuel gas pressure control device (promoting to control starting device A (S44) by water conveying) operation.This starting device A (S44) operates fuel gas volume control device and/or fuel gas pressure control device one or many, until by decision maker C (namely, drop measurement) till (S45) judge the water shortage near oxidant gas flow paths outlet, now based on described judgement (promoting to control arresting stop A by water conveying) shut-down operation.Next, oxidizer gas flow rate control device and/or oxidant gas pressure control device (by water conveying inhibitory control starting device A (S46)) operation.This starting device A (S46) operating oxidizer gas flow control device and/or oxidant gas pressure control device one or many, until by decision maker D (namely, drop measurement) till (S47) judge the hypervolia near oxidant gas flow paths outlet, now based on described judgement (by water conveying inhibitory control arresting stop A) shut-down operation.Finally, judge that whether the water yield near oxidant gas flow paths entrance is not enough by decision maker A (that is, resistance measurement).If water shortage, then water conveying promotes that controlling starting device A (S44) operates fuel gas volume control device and/or fuel gas pressure control device again.On the other hand, if the water yield is not not enough, then the operation of fuel cell proceeds (S49).
By the fuel cell system with this structure, when judging the water shortage near oxidant gas flow paths entrance, after the conveying of use water promotes that controlling starting device A promotes that water is transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet, by using water conveying inhibitory control starting device A to be increased in the water yield near oxidant gas flow paths outlet, both not many also not suitable water yields very little can be maintained near oxidant gas flow paths entrance and exit.And, by fuel cell system of the present invention, can, based on the result from the final decision maker A of the not enough water yield, by again repeating series of steps, prevent the water in whole oxidant gas flow paths from distributing unevenly.
From identical viewpoint, the pattern of the method for operation of fuel cell of the present invention can be constructed as follows.Namely, if it is determined that the water shortage near oxidant gas flow paths entrance, then the stoichiometric proportion of fuel gas increases to and is more than or equal to 1.0 and is less than or equal in the scope of 10 by one or many, and/or is reduced to by fuel gas pressure and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa.Then, after judging the water shortage near oxidant gas flow paths outlet, stop fuel gas controlling.Next, the stoichiometric proportion of oxidant gas is reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0 by one or many, and/or is increased to by oxidant gas pressure and be more than or equal to atmospheric pressure and be less than or equal in the scope of 0.3MPa.Then, after judging the hypervolia near oxidant gas flow paths outlet, stop oxidant gas controlling.If after this judge the water shortage near oxidant gas flow paths entrance, then again start fuel gas and control.On the other hand, if it is determined that the water yield near oxidant gas flow paths entrance is not not enough, then the operation of fuel cell is continued.
The another kind of pattern of fuel cell system of the present invention comprises: I) fuel gas control device; II) oxidant gas control device; III) decision maker A and/or decision maker C; IV) decision maker B and/or decision maker D; V) water conveying inhibitory control starting device B; VI) water conveying inhibitory control arresting stop B; VII) water conveying promotion control starting device B; VIII) water conveying promotion control arresting stop B; And IV) the final decision maker B of the not enough water yield.After judging the water shortage near oxidant gas flow paths entrance by decision maker A and/or C, water conveying inhibitory control starting device B operating oxidizer gas control equipment one or many.After water conveying inhibitory control starting device B operating oxidizer gas control equipment, after judged the hypervolia near oxidant gas flow paths outlet by decision maker B and/or D, water conveying inhibitory control arresting stop B stops oxidant gas control device.After water conveying inhibitory control arresting stop B stops oxidant gas control device, water conveying promotes that controlling starting device B operates fuel gas control device one or many.After judged the water shortage near oxidant gas flow paths outlet by decision maker A and/or C, water conveying promotes to control all elements that arresting stop B stops fuel gas control device.After water conveying promotes that controlling arresting stop B stops all elements of fuel gas control device, if judge the water shortage near oxidant gas flow paths entrance by decision maker A and/or C, then the final decision maker B of the not enough water yield makes water carry inhibitory control starting device B operating oxidizer gas control equipment again, and if judge that the water yield near oxidant gas flow paths entrance is not not enough by decision maker A and/or C, then the final decision maker B of the not enough water yield continues operation of fuel cells.
Fig. 9 is the flow chart of the program of the 6th typical case that preferred fuel cell system is shown, for the method for operation performing fuel cell of the present invention.Now, will suppose that wherein fuel cell system is the situation (S51) operated constantly under high loads.Until measure coolant temperature T and decision maker A and operate from this state, identical with the 5th above-mentioned typical case (Fig. 8).
If resistance value R is greater than set point R 1then decision maker A (S53) judges the water shortage near oxidant gas flow paths entrance, and oxidizer gas flow rate control device and/or oxidant gas pressure control device (by water conveying inhibitory control starting device B) operation (S54).This starting device B operating oxidizer gas flow control device and/or oxidant gas pressure control device one or many, until by decision maker D (namely, drop measurement) till (S55) judge the hypervolia near oxidant gas flow paths outlet, now based on described judgement (by water conveying inhibitory control arresting stop B) shut-down operation.Next, fuel gas volume control device and/or fuel gas pressure control device (promoting to control starting device B by water conveying) (S56) operation.This starting device B (S56) operates fuel gas volume control device and/or fuel gas pressure control device one or many, until by decision maker C (namely, drop measurement) till (S57) judge the water shortage near oxidant gas flow paths outlet, now based on described judgement (promoting to control arresting stop B by water conveying) shut-down operation.Finally, judge that whether the water yield near oxidant gas flow paths entrance is not enough by decision maker A (that is, resistance measurement).If water shortage, then water conveying inhibitory control starting device B (S54) operating oxidizer gas flow control device and/or oxidant gas pressure control device again.On the other hand, if the water yield is not not enough, then the operation of fuel cell proceeds (S59).
By the fuel cell system with this structure, when judging the water shortage near oxidant gas flow paths entrance, water is suppressed to be transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet by using water conveying inhibitory control starting device B, and assembled the water having q.s near oxidant gas flow paths outlet after, water conveying is used to promote control starting device B and promote that water is transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet, both not many also not suitable water yields very little can be maintained near oxidant gas flow paths entrance and exit.And, by fuel cell system of the present invention, can, based on the result from the final decision maker B of the not enough water yield, by again repeating series of steps, prevent the water in whole oxidant gas flow paths from distributing unevenly.
From identical viewpoint, the pattern of the method for operation of fuel cell of the present invention can be constructed as follows.Namely, if it is determined that the water shortage near oxidant gas flow paths entrance, then the stoichiometric proportion of oxidant gas is reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0 by one or many, and/or is increased to by oxidant gas pressure and be more than or equal to atmospheric pressure and be less than or equal in the scope of 0.3MPa.Then, after judging the hypervolia near oxidant gas flow paths outlet, stop oxidant gas controlling.Next, the stoichiometric proportion of fuel gas increases to and is more than or equal to 1.0 and is less than or equal in the scope of 10 by one or many, and/or is reduced to by fuel gas pressure and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa.Then, after judging the water shortage near oxidant gas flow paths outlet, stop fuel gas controlling.If after this judge the water shortage near oxidant gas flow paths entrance, then again start oxidant gas and control.On the other hand, if it is determined that the water yield near oxidant gas flow paths entrance is not not enough, then the operation of fuel cell is continued.
Another pattern of fuel cell system of the present invention comprises: I) fuel gas control device; II) oxidant gas control device; III) decision maker A and/or decision maker C; IV) decision maker B and/or decision maker D; V) promote to control starting device little over the conveying of many water; VI) promote to control arresting stop little over the conveying of many water; VII) water conveying inhibitory control starting device C; VIII) water conveying inhibitory control arresting stop C; IV) water conveying promotion control starting device C; And X) water conveying promotion control arresting stop C.Promote to control starting device operation fuel gas control device one or many little over the conveying of many water.After promote to control starting device operation fuel gas control device little over the conveying of many water, after judged the water shortage near oxidant gas flow paths outlet by decision maker A and/or C, promote that controlling arresting stop stops fuel gas control device little over the conveying of many water.After promoting that controlling arresting stop stops fuel gas control device little over the conveying of many water, water conveying inhibitory control starting device C operating oxidizer gas control equipment.After judged the hypervolia near oxidant gas flow paths outlet by decision maker B and/or D, water conveying inhibitory control arresting stop C stops all elements of oxidant gas control device.After water conveying inhibitory control arresting stop C stops all elements of oxidant gas control device, water conveying promotes that controlling starting device C operates fuel gas control device.After water conveying promotes that controlling starting device C operates fuel gas control device, if judge the water shortage near oxidant gas flow paths outlet by decision maker A and/or C, then water conveying promotes that controlling arresting stop C makes water carry inhibitory control starting device C operating oxidizer gas control equipment again, and if judge that the water yield near oxidant gas flow paths outlet is not not enough by decision maker A and/or C, then water conveying promotes that controlling arresting stop C stops fuel gas control device and continue operation of fuel cells.
Figure 10 is the flow chart of the program of the 7th typical case that preferred fuel cell system is shown, for the method for operation performing fuel cell of the present invention.Now, will suppose that wherein fuel cell system is the situation (S61) operated constantly under high loads.During operation, within every 10 seconds to 10 minutes, coolant temperature T (S62) is measured by above-mentioned coolant temperature measurement mechanism.Now, if the coolant temperature T measured is equal to or less than set point T 1, then operation proceeds (S61).On the other hand, if coolant temperature T is greater than set point T 1, then fuel gas volume control device and/or fuel gas pressure control device (by promoting to control starting device little over the conveying of many water) (S63) operation.This starting device (S63) operates fuel gas volume control device and/or fuel gas pressure control device one or many, until by decision maker A (namely, resistance measurement) (S64) judge oxidant gas flow paths outlet near water shortage till, now based on described judgement (by little over many water conveying promote control arresting stop) shut-down operation.Namely, after certain exception in a fuel cell has been determined earlier by coolant temperature measurement mechanism (S62), when not judging the position of the exception in oxidant gas flow paths, operating procedure up to this point, only be transported near oxidant gas flow paths entrance by fuel gas flow path near oxidant gas flow paths outlet little over many water yields temporarily by promotion, and make the water shortage near oxidant gas flow paths outlet.
After promoting that controlling arresting stop stops fuel gas volume control device and/or fuel gas pressure control device little over the conveying of many water, oxidizer gas flow rate control device and/or oxidant gas pressure control device (by water conveying inhibitory control starting device C) (S65) operation.This starting device C operating oxidizer gas flow control device and/or oxidant gas pressure control device one or many, until by decision maker B (namely, voltage measurement) till (S66) judge the hypervolia near oxidant gas flow paths outlet, now based on described judgement (by water conveying inhibitory control arresting stop C) shut-down operation.Next, fuel gas volume control device and/or fuel gas pressure control device (promoting to control starting device C by water conveying) (S67) operation.Finally, judge that whether the water yield near oxidant gas flow paths outlet is not enough by decision maker A (that is, resistance measurement) (S68).If water shortage, then water conveying inhibitory control starting device C (S65) operating oxidizer gas flow control device and/or oxidant gas pressure control device again.On the other hand, if the water yield is not not enough, then the operation of fuel cell proceeds (S69).
By the fuel cell system with this structure, promote that controlling starting device makes the water yield near oxidant gas flow paths outlet suitably not enough by first using little over the conveying of many water, then use water conveying inhibitory control starting device C and suppress water to be transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet, and assembled the water having q.s near oxidant gas flow paths outlet after, controlling starting device C promotes that water is delivered near oxidant gas flow paths entrance near oxidant gas flow paths outlet to use water conveying to promote, both not many also not suitable water yields very little can be maintained near oxidant gas flow paths entrance and exit.And, just the catalyst layer of its original performance can not be maintained (such as once become wet when fuel cell system of the present invention comprises having, this catalyst layer: the small aperture wherein in catalyst layer is got clogged by oxidation catalyst wittingly) fuel cell time, fuel cell system of the present invention is especially effective, this is because this fuel cell system can not allow catalyst layer become wet.
From identical viewpoint, the another kind of pattern of the method for operation of fuel cell of the present invention can be constructed as follows.That is, the stoichiometric proportion of fuel gas increases to and is more than or equal to 1.0 and is less than or equal in the scope of 10 by one or many, and/or is reduced to by fuel gas pressure and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa.Then, after judging the water shortage near oxidant gas flow paths outlet, stop fuel gas controlling.Then, the stoichiometric proportion of oxidant gas is reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0 by one or many, and/or is increased to by oxidant gas pressure and be more than or equal to atmospheric pressure and be less than or equal in the scope of 0.3MPa.Then, after judging the hypervolia near oxidant gas flow paths outlet, stop oxidant gas controlling.Then, the stoichiometric proportion of fuel gas is increased to and is more than or equal to 1.0 and is less than or equal in the scope of 10, and/or fuel gas pressure is reduced to is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa.If after this judge the water shortage near oxidant gas flow paths outlet, then again start oxidant gas and control.On the other hand, if it is determined that the water yield near oxidant gas flow paths outlet is not not enough, then fuel gas is stopped to control and continue operation of fuel cells.
Another pattern of fuel cell system of the present invention comprises: I) fuel gas control device; II) oxidant gas control device; III) decision maker A and/or decision maker C; IV) decision maker B and/or decision maker D; V) little over many water conveying inhibitory control starting device; VI) little over many water conveying inhibitory control arresting stop; VII) water conveying promotion control starting device D; VIII) water conveying promotion control arresting stop D; IV) water conveying inhibitory control starting device D; And X) water conveying inhibitory control arresting stop D.Little over many water conveying inhibitory control starting device operating oxidizer gas control equipment one or many.After little over many water conveying inhibitory control starting device operating oxidizer gas control equipment, after judged the hypervolia near oxidant gas flow paths outlet by decision maker B and/or D, stop oxidant gas control device little over many water conveying inhibitory control arresting stop.After stopping oxidant gas control device little over many water conveying inhibitory control arresting stop, water conveying promotes that controlling starting device D operates fuel gas control device.After judged the water shortage near oxidant gas flow paths outlet by decision maker A and/or C, water conveying promotes to control all elements that arresting stop D stops fuel gas control device.After water conveying promotes that controlling arresting stop D stops all elements of fuel gas control device, water conveying inhibitory control starting device D operating oxidizer gas control equipment.After water conveying inhibitory control starting device D operating oxidizer gas control equipment, if judge the hypervolia near oxidant gas flow paths outlet by decision maker B and/or D, then water conveying inhibitory control arresting stop D makes water carry promotion to control starting device D and again operates fuel gas control device, and if judge that the water yield near oxidant gas flow paths outlet is not too much by decision maker B and/or D, then water conveying inhibitory control arresting stop D stops oxidant gas control device and continues operation of fuel cells.
Figure 11 is the flow chart of the program of the 8th typical case that preferred fuel cell system is shown, for the method for operation performing fuel cell of the present invention.Now, will suppose that wherein fuel cell system is the situation (S71) operated constantly under high loads.During operation, within every 10 seconds to 10 minutes, coolant temperature T (S72) is measured by above-mentioned coolant temperature measurement mechanism.Now, if the coolant temperature T measured is equal to or less than set point T 1, then operation proceeds (S71).On the other hand, if coolant temperature T is greater than set point T 1, then oxidizer gas flow rate control device and/or oxidant gas pressure control device (by little over many water conveying inhibitory control starting device) (S73) operation.This starting device (S73) operating oxidizer gas flow control device and/or oxidant gas pressure control device one or many, until by decision maker B (namely, voltage measurement) till (S74) judge the hypervolia near oxidant gas flow paths outlet, now based on described judgement (by little over many water conveying inhibitory control arresting stop) shut-down operation.Namely, after certain exception in a fuel cell has been determined earlier by coolant temperature measurement mechanism (S72), when not judging the position of the exception in oxidant gas flow paths, operating procedure up to this point, only be transported near oxidant gas flow paths entrance by fuel gas flow path near oxidant gas flow paths outlet little over many water yields temporarily by suppression, and make the hypervolia near oxidant gas flow paths outlet.
After stopping oxidizer gas flow rate control device and/or oxidant gas pressure control device little over many water conveying inhibitory control arresting stop, fuel gas volume control device and/or fuel gas pressure control device (promoting to control starting device D by water conveying) (S75) operation.This starting device D operates fuel gas volume control device and/or fuel gas pressure control device one or many, until by decision maker A (namely, resistance measurement) till (S76) judge the water shortage near oxidant gas flow paths outlet, now based on described judgement (promoting to control arresting stop D by water conveying) shut-down operation.Next, oxidizer gas flow rate control device and/or oxidant gas pressure control device (by water conveying inhibitory control starting device D) (S77) operation.Finally, judge that whether the water yield near oxidant gas flow paths outlet is too much by decision maker B (that is, voltage measurement) (S78).If hypervolia, then water conveying promotes that controlling starting device D (S75) operates fuel gas volume control device and/or fuel gas pressure control device again.On the other hand, if the water yield is not too much, then the operation of fuel cell proceeds (S79).
By the fuel cell system with this structure, make the water yield near oxidant gas flow paths outlet suitably too much by first using little over many water conveying inhibitory control starting device, then water conveying is used to promote control starting device D and promote that water is transported near oxidant gas flow paths entrance near oxidant gas flow paths outlet, and then use water conveying inhibitory control starting device D is increased in the water yield near oxidant gas flow paths outlet, both not many also not suitable water yields very little can be maintained near oxidant gas flow paths entrance and exit.And, when fuel cell system of the present invention comprise have just can not maintain its original performance once become dry dielectric film (such as, cross carbon fluoro sulfonate dielectric film) fuel cell time, fuel cell system of the present invention is especially effective, this is because this fuel cell system can not allow dielectric film become dry.
From identical viewpoint, the pattern of the method for operation of fuel cell of the present invention can be constructed as follows.That is, the stoichiometric proportion of oxidant gas is reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0 by one or many, and/or is increased to by oxidant gas pressure and be more than or equal to atmospheric pressure and be less than or equal in the scope of 0.3MPa.Then, after judging the hypervolia near oxidant gas flow paths outlet, stop oxidant gas controlling.Next, the stoichiometric proportion of fuel gas increases to and is more than or equal to 1.0 and is less than or equal in the scope of 10 by one or many, and/or is reduced to by fuel gas pressure and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa.Then, after judging the water shortage near oxidant gas flow paths outlet, stop fuel gas controlling.Next, the stoichiometric proportion of oxidant gas is reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0, and/or oxidant gas pressure is increased to be more than or equal to atmospheric pressure and be less than or equal in the scope of 0.3MPa.If after this judge the hypervolia near oxidant gas flow paths outlet, then again start fuel gas and control.On the other hand, if it is determined that the water yield near oxidant gas flow paths outlet is not too much, then stops oxidant gas controlling and continue the operation of fuel cell.
By fuel cell of the present invention method of operation and be preferably used for the fuel cell system performing this method of operation, water near oxidant gas flow paths outlet has been transported near fuel gas flow path entrance by polymer dielectric film after, by the more water yield in fuel gas being transported near fuel gas flow path outlet, the more water yield can be transported near oxidant gas flow paths entrance by polymer dielectric film near fuel gas flow path outlet.Therefore, the water yield near oxidant gas flow paths entrance and the water yield near oxidant gas flow paths outlet can be regulated, trend towards in the prior art near described oxidant gas flow paths entrance becoming dry, trend towards in the prior art becoming wet near described oxidant gas flow paths outlet.As a result, when can work as under the condition of non-humidification and/or under the condition of high temperature, anti-sealing is distributed on the surface of monocell unevenly.And fuel cell system of the present invention has decision maker, so the water shortage near oxidant gas flow paths entrance can be determined exactly.
By fuel cell of the present invention preferred method of operation and be preferably used for the fuel cell system performing this method of operation, water near oxidant gas flow paths outlet has been transported near fuel gas flow path entrance by polymer dielectric film after, by the more water yield in fuel gas being transported near fuel gas flow path outlet, the more water yield can be transported near oxidant gas flow paths entrance by polymer dielectric film near fuel gas flow path outlet.Therefore, the water yield near oxidant gas flow paths entrance and the water yield near oxidant gas flow paths outlet can be regulated, the described water yield near oxidant gas flow paths entrance trends towards becoming dry in the prior art, trends towards in the prior art becoming wet near described oxidant gas flow paths outlet.As a result, when can work as under the condition of non-humidification and/or under the condition of high temperature, anti-sealing is distributed on the surface of monocell unevenly.And, according to the present invention, by suppress to be taken away by oxidant gas and be discharged into the water yield of the outside of fuel cell system of the present invention, water can be gathered near oxidant gas flow paths outlet.In addition, fuel cell system of the present invention has decision maker, so can determine the water shortage or too much near oxidant gas flow paths entrance and exit exactly.
Next, by illustrated example.Below by the measurement of the power generation performance of change of the fuel gas scale of construction explained along with supply, dewpoint humidity and pressure drop.For the monocell with above-mentioned membrane electrode assembly, measure cell voltage E (V), cell resistance R (m Ω × cm 2), anode export dewpoint humidity (%), cathode outlet dewpoint humidity (%), hydrogen pressure drop (kPa) and air-pressure drop (kPa) be relative to the change of change of stoichiometric proportion of hydrogen being used as fuel gas, in described monocell, fuel gas flow path and oxidant gas flow paths are arranged so that fuel gas (namely, hydrogen) and oxidant gas (that is, air) flow along contrary direction.Specific test condition is as follows.
Current density: 1.0A/cm 2
Coolant outlet temperature: 80 DEG C
Hydrogen flowing quantity: little by little increase to the stoichiometric proportion of 1.2 to 6.0, and measured
Air mass flow: measure at the stoichiometric proportion place of 1.3,1.5 and 1.6 respectively
Gas pressure: be all 200kPa × Abs for both hydrogen and air
Gas flow paths inlet humidification: do not have moisture in hydrogen flow path or inlet air flow path.
Figure 12 is the chart illustrating that cell voltage changes along with the change of the stoichiometric proportion of hydrogen, and Figure 13 is the chart illustrating that cell resistance changes along with the change of the stoichiometric proportion of hydrogen.When air stoichiometry ratio is 1.3, the white ringlet designation data in chart.When air stoichiometry ratio is 1.5, the white box designation data in chart, and when air stoichiometry ratio is 1.6, the white triangles shape designation data in chart.As shown in Figure 12, at all stoichiometric proportion places, that is, at the stoichiometric proportion place of 1.3,1.5 and 1.6, when the stoichiometric proportion of hydrogen is about 2.5, cell voltage has local maximum.And as shown in Figure 13, the air stoichiometry 1.5 and 1.6 is than place, and when the stoichiometric proportion of hydrogen is about 2.5, cell resistance has local minimum.
Figure 14 is the chart illustrating that the dewpoint humidity at anode export place changes along with the change of the stoichiometric proportion of hydrogen, and Figure 15 is the chart illustrating that the dewpoint humidity at cathode outlet place changes along with the change of the stoichiometric proportion of hydrogen.White ringlet in chart, white box and white triangles shape are as the same ground designation data in Figure 12 and 13.Some from the anode row of fuel gas flow path outlet drain discharges water are by being transported to the oxidant gas flow paths entrance on the opposite side of dielectric film through dielectric film.Therefore, by checking anode export dewpoint humidity, the water yield in oxidant gas flow paths porch can be known.And, by checking cathode outlet dewpoint humidity, the water yield in oxidant gas flow paths exit can be known.As shown in Figure 14, the air stoichiometry 1.5 and 1.6 is than place, and when the stoichiometric proportion of hydrogen is about 2.5, anode export dewpoint humidity has local maximum.Incidentally, when air stoichiometry ratio is 1.3 (that is, white ringlet), even when hydrogen stoichiometric is than when increasing, anode export dewpoint humidity keep saturated while maintain higher humidity.And, as shown in Figure 15, in each air stoichiometry than place, that is, at the air stoichiometry ratio place of 1.3,1.5 and 1.6, when the stoichiometric proportion of hydrogen is about 2.5, the chart of the cathode outlet dewpoint humidity reduced substantially monotonously there is flex point.
Figure 16 is the chart illustrating that hydrogen pressure drop changes along with the change of the stoichiometric proportion of hydrogen.Incidentally, now air stoichiometry ratio is 1.5.From this chart, be apparent that, the stoichiometric proportion of hydrogen pressure drop and hydrogen increases pro rata.
Figure 17 is the chart illustrating that air-pressure drop changes along with the change of the stoichiometric proportion of hydrogen.Incidentally, now air stoichiometry ratio is 1.6.From this chart, being apparent that, reducing tempestuously at the hydrogen stoichiometric being about 2.5 than place's air-pressure drop, is the highest at the described hydrogen stoichiometric being about 2.5 than place's voltage and resistance value, as mentioned above.
Now by the fuel gas scale of construction of inspection supply in power generation performance and water be distributed in unevenly on the surface of monocell in effect.Measure from above-mentioned power generation performance, be apparent that, when the stoichiometric proportion of hydrogen is when being more than or equal to 1.5 and in the scope being less than or equal to 3.0, obtain best power generation performance, this is because obtain the local maximum of cell voltage when stoichiometric proportion is about 2.5, and also obtain the local minimum of cell resistance when stoichiometric proportion is about 2.5.And, measure from above-mentioned dewpoint humidity, be apparent that, when the stoichiometric proportion of hydrogen is when being more than or equal to 1.0 and in the scope being less than or equal to 4.0, obtain from fuel gas flow path by dielectric film to the best increase efficiency in the water yield of oxidant gas flow paths, this is because obtain local maximum when stoichiometric proportion is about 2.5 on the chart of anode export dewpoint humidity, and also on the chart of cathode outlet dewpoint humidity, has flex point when stoichiometric proportion is about 2.5.In addition, from above-mentioned drop measurement, being apparent that, reducing tempestuously at the hydrogen stoichiometric being about 2.5 than place's air-pressure drop, is also the highest at the described hydrogen stoichiometric being about 2.5 than place's voltage and resistance value, as mentioned above.Therefore, can relative to supply the fuel gas scale of construction in power generation performance, in gas pressure drop and water be distributed in unevenly on the surface of monocell in effect and consider following content.
When the stoichiometric proportion of hydrogen is less than 1.0, the discharge reduction taken away by hydrogen, has interrupted the circulation of the water shown in Fig. 2.As a result, water becomes and is distributed on the surface of monocell unevenly, causes power generation performance to reduce.In addition, the water of uneven distribution causes the partial occlusion of oxidant gas flow paths, increases air-pressure drop.And if the stoichiometric proportion of hydrogen is more than 4.0, then the water yield taken away by hydrogen increases more than necessary, the dielectric film in fuel gas flow path porch is become dry.As a result, from oxidant gas flow paths outlet by the discharge reduction of dielectric film to fuel gas flow path entrance, power generation performance is caused to reduce.In addition, the minimizing in the water yield causes oxidant gas flow paths to become dry, thus air-pressure drop is reduced.
Thus, in the exemplary embodiment, by measuring the power generation performance of change of the amount of the fuel gas along with supply, dewpoint humidity and pressure drop, be apparent that, when the stoichiometric proportion of the hydrogen of the fuel gas as a kind of type is in the scope of 1.0 to 4.0, the water yield near oxidant gas flow paths entrance can increase, and when not making dielectric film become dry, enables the decline of power generation performance suppressed.

Claims (34)

1. one kind is provided with the fuel cell system of fuel cell, described fuel cell has heap, described heap has monocell, described monocell comprises membrane electrode assembly, in described membrane electrode assembly, polymer dielectric film is clipped between pair of electrodes, and fuel gas and oxidant gas are supplied to described fuel cell by described membrane electrode assembly, and in I) do not have moist condition or II) temperature of described membrane electrode assembly operates under at least one condition in the condition of at least 70 DEG C, it is characterized in that
Described fuel cell has fuel gas flow path on the side of described membrane electrode assembly, and has oxidant gas flow paths on the opposite side of described membrane electrode assembly; And
Described fuel gas flow path and described oxidant gas flow paths are arranged so that described fuel gas and described oxidant gas relative to each other flow along contrary direction on described membrane electrode assembly, described fuel gas flow path comprises fuel gas flow path entrance and fuel gas flow path outlet, further, described oxidant gas flow paths comprises oxidant gas flow paths entrance and oxidant gas flow paths outlet;
Described fuel cell system is configured to the uneven distribution of anti-sealing on battery surface, and comprises:
Judge the decision maker of the water yield near oxidant gas flow paths entrance; With
Fuel gas control device, if judge the water shortage near described oxidant gas flow paths entrance by described decision maker, then described fuel gas control device is increased in the water yield near described oxidant gas flow paths entrance by increasing fuel gas flow and/or reducing fuel gas pressure.
2. fuel cell system according to claim 1, is characterized in that,
Described decision maker judges the water yield near described oxidant gas flow paths outlet, and
If described decision maker judges the hypervolia near described oxidant gas flow paths outlet, then described fuel gas control device increases described fuel gas flow and/or reduces described fuel gas pressure, to be increased in the water yield near described oxidant gas flow paths entrance.
3. fuel cell system according to claim 1, is characterized in that,
Described decision maker judges the water yield near described oxidant gas flow paths outlet, and
Described fuel cell system comprises oxidant gas control device, if described decision maker judges the water shortage near described oxidant gas flow paths entrance and/or the water shortage near described oxidant gas flow paths outlet, then described oxidant gas control device reduces described oxidizer gas flow rate and/or increases described oxidant gas pressure, to reduce the water yield of being taken out of from described battery by described oxidant gas and to increase the water yield that can be transported to described fuel gas flow path entrance side from described oxidant gas flow paths outlet side.
4. fuel cell system according to any one of claim 1 to 3, it is characterized in that, described decision maker is decision maker A, described decision maker A measures the resistance value of whole described fuel cell, and when 105% of the minimum value of the resistance measured in advance of the described monocell at each temperature that described resistance value exceedes in multiple temperature and/or described heap, judge the water shortage near described oxidant gas flow paths entrance and/or the water shortage near described oxidant gas flow paths outlet.
5. fuel cell system according to any one of claim 1 to 3, it is characterized in that, described decision maker is decision maker B, described decision maker B measures resistance value and the voltage of whole described fuel cell, and when 105% of described minimum value of the resistance measured in advance described in described resistance value is less than and 95% of the maximum of the voltage measured in advance of the described monocell at described voltage is less than in multiple temperature each temperature and/or described heap time, judge the hypervolia near described oxidant gas flow paths entrance and/or the hypervolia near described oxidant gas flow paths outlet.
6. fuel cell system according to any one of claim 1 to 3, it is characterized in that, described decision maker is decision maker C, the pressure drop of the oxidant gas of described oxidant gas flow paths is flow through in described decision maker C measurement, and when described pressure drop is less than 105% of the minimum value of the pressure drop of measuring in advance of the oxidant gas flowing through described oxidant gas flow paths, judge the water shortage near described oxidant gas flow paths entrance and/or the water shortage near described oxidant gas flow paths outlet.
7. fuel cell system according to any one of claim 1 to 3, it is characterized in that, described decision maker is decision maker D, the pressure drop of the oxidant gas of described oxidant gas flow paths is flow through in described decision maker D measurement, and when described pressure drop exceedes 105% of the maximum of the pressure drop of measuring in advance of the oxidant gas flowing through described oxidant gas flow paths, judge the hypervolia near described oxidant gas flow paths entrance and/or the hypervolia near described oxidant gas flow paths outlet.
8. fuel cell system according to any one of claim 1 to 3, it is characterized in that, near described fuel gas flow path outlet, be provided with fuel gas pressure adjuster valve, and described fuel gas control device is the fuel gas pressure control device reducing described fuel gas pressure by regulating described fuel gas pressure adjuster valve.
9. fuel cell system according to claim 6, it is characterized in that, described fuel gas pressure control device regulates described fuel gas pressure adjuster valve, is more than or equal to atmospheric pressure to be reduced to by described fuel gas pressure and to be less than or equal in the scope of 0.3MPa.
10. want the fuel cell system according to any one of 4 to 7 according to right, it is characterized in that, also be provided with oxidant gas feedway, and described oxidant gas control device is the oxidizer gas flow rate control device reducing described oxidizer gas flow rate by regulating described oxidant gas feedway.
11. fuel cell systems according to claim 10, it is characterized in that, described oxidizer gas flow rate control device regulates described oxidant gas feedway, is more than or equal to 1.0 the stoichiometric proportion of described oxidant gas to be reduced to and to be less than or equal in the scope of 3.0.
12. fuel cell systems according to claim 1, is characterized in that, described fuel cell system also comprises:
Fuel gas feeding device, its by fuel gas supply to described fuel cell,
Wherein, described fuel gas control device is the fuel gas volume control device increasing described fuel gas flow by regulating described fuel gas feeding device.
13. fuel cell systems according to claim 12, it is characterized in that, described fuel gas volume control device regulates described fuel gas feeding device, is more than or equal to 1.0 the stoichiometric proportion of described fuel gas to be increased to and is less than or equal in the scope of 10.
14. fuel cell systems according to claim 1, is characterized in that, described fuel cell system also comprises:
Oxidant gas pressure adjuster valve, it is arranged near the outlet of described oxidant gas flow paths, and regulates the pressure of described oxidant gas,
Wherein, described oxidant gas control device is the oxidant gas pressure control device increasing described oxidant gas pressure by regulating described oxidant gas pressure adjuster valve.
15. fuel cell systems according to claim 14, it is characterized in that, described oxidant gas pressure control device regulates described oxidant gas pressure adjuster valve, is more than or equal to atmospheric pressure to be increased to by described oxidant gas pressure and to be less than or equal in the scope of 0.3MPa.
16. fuel cell systems according to any one of claim 4 to 7, it is characterized in that, described fuel cell system comprises:
Described fuel gas control device;
Described oxidant gas control device;
Decision maker A according to claim 3 and/or decision maker C according to claim 5;
Decision maker B according to claim 4 and/or decision maker D according to claim 6;
Water conveying promotes to control starting device A, after judging the water shortage near described oxidant gas flow paths entrance by described decision maker A and/or C, described water conveying promotes that controlling starting device A operates described fuel gas control device one or many;
Water conveying promotes to control arresting stop A, after described water conveying promotes that controlling starting device A operates described fuel gas control device, after judged the water shortage near described oxidant gas flow paths outlet by described decision maker A and/or C, described water conveying promotes that controlling arresting stop A stops described fuel gas control device;
Water conveying inhibitory control starting device A, after described water conveying promotes that controlling arresting stop A stops described fuel gas control device, described water conveying inhibitory control starting device A operates described oxidant gas control device one or many;
Water conveying inhibitory control arresting stop A, after judged the hypervolia near described oxidant gas flow paths outlet by described decision maker B and/or D, described water conveying inhibitory control arresting stop A stops all elements of described oxidant gas control device; And
The final decision maker A of the not enough water yield, after described water conveying inhibitory control arresting stop A stops all elements of described oxidant gas control device, if judge the water shortage near described oxidant gas flow paths entrance by described decision maker A and/or C, then the described not enough water yield final decision maker A makes described water carry promotion to control starting device A and again operates described fuel gas control device, and if judge that the water yield near described oxidant gas flow paths entrance is not not enough by described decision maker A and/or C, then the described not enough water yield final decision maker A continues the described fuel cell of operation.
17. fuel cell systems according to any one of claim 4 to 7, it is characterized in that, described fuel cell system comprises:
Described fuel gas control device;
Described oxidant gas control device;
Decision maker A according to claim 3 and/or decision maker C according to claim 5;
Decision maker B according to claim 4 and/or decision maker D according to claim 6;
Water conveying inhibitory control starting device B, after judging the water shortage near described oxidant gas flow paths entrance by described decision maker A and/or C, described water conveying inhibitory control starting device B operates described oxidant gas control device one or many;
Water conveying inhibitory control arresting stop B, after described water conveying inhibitory control starting device B operates described oxidant gas control device, after judged the hypervolia near described oxidant gas flow paths outlet by described decision maker B and/or D, described water conveying inhibitory control arresting stop B stops described oxidant gas control device;
Water conveying promotes to control starting device B, and after described water conveying inhibitory control arresting stop B stops described oxidant gas control device, described water conveying promotes that controlling starting device B operates described fuel gas control device one or many;
Water conveying promotes to control arresting stop B, after judged the water shortage near described oxidant gas flow paths outlet by described decision maker A and/or C, described water conveying promotes to control all elements that arresting stop B stops described fuel gas control device; And
The final decision maker B of the not enough water yield, after described water conveying promotes that controlling arresting stop B stops all elements of described fuel gas control device, if judge the water shortage near described oxidant gas flow paths entrance by described decision maker A and/or C, then the described not enough water yield final decision maker B makes described water carry inhibitory control starting device B again to operate described oxidant gas control device, and if judge that the water yield near described oxidant gas flow paths entrance is not not enough by described decision maker A and/or C, then the described not enough water yield final decision maker B continues the described fuel cell of operation.
18. fuel cell systems according to any one of claim 4 to 7, it is characterized in that, described fuel cell system comprises:
Described fuel gas control device;
Described oxidant gas control device;
Decision maker A according to claim 3 and/or decision maker C according to claim 5;
Decision maker B according to claim 4 and/or decision maker D according to claim 6;
Promote to control starting device little over the conveying of many water, it operates described fuel gas control device one or many;
Promote to control arresting stop little over the conveying of many water, to promote to control after starting device operates described fuel gas control device little over the conveying of many water described, after judged the water shortage near described oxidant gas flow paths outlet by described decision maker A and/or C, described conveying little over many water promotes that controlling arresting stop stops described fuel gas control device;
Water conveying inhibitory control starting device C, described promote that controlling arresting stop stops described fuel gas control device little over the conveying of many water after, described water conveying inhibitory control starting device C operates described oxidant gas control device;
Water conveying inhibitory control arresting stop C, after judged the hypervolia near described oxidant gas flow paths outlet by described decision maker B and/or D, described water conveying inhibitory control arresting stop C stops all elements of described oxidant gas control device;
Water conveying promotes to control starting device C, and after described water conveying inhibitory control arresting stop C stops all elements of described oxidant gas control device, described water conveying promotes that controlling starting device C operates described fuel gas control device; And
Water conveying promotes to control arresting stop C, after described water conveying promotes that controlling starting device C operates described fuel gas control device, if judge the water shortage near described oxidant gas flow paths outlet by described decision maker A and/or C, then described water conveying promotes that controlling arresting stop C makes described water carry inhibitory control starting device C again to operate described oxidant gas control device, and if judge that the water yield near described oxidant gas flow paths outlet is not not enough by described decision maker A and/or C, then described water conveying promotes that controlling arresting stop C stops described fuel gas control device and continue the described fuel cell of operation.
19. fuel cell systems according to any one of claim 4 to 7, it is characterized in that, described fuel cell system comprises:
Described fuel gas control device;
Described oxidant gas control device;
Decision maker A according to claim 3 and/or decision maker C according to claim 5;
Decision maker B according to claim 4 and/or decision maker D according to claim 6;
Little over many water conveying inhibitory control starting device, it operates described oxidant gas control device one or many;
Little over many water conveying inhibitory control arresting stop, described operate described oxidant gas control device little over many water conveying inhibitory control starting device after, after judged the hypervolia near described oxidant gas flow paths outlet by described decision maker B and/or D, describedly stop described oxidant gas control device little over many water conveying inhibitory control arresting stop;
Water conveying promotes to control starting device D, described stop described oxidant gas control device little over many water conveying inhibitory control arresting stop after, described water conveying promotes that controlling starting device D operates described fuel gas control device;
Water conveying promotes to control arresting stop D, after judged the water shortage near described oxidant gas flow paths outlet by described decision maker A and/or C, described water conveying promotes to control all elements that arresting stop D stops described fuel gas control device;
Water conveying inhibitory control starting device D, after described water conveying promotes that controlling arresting stop D stops all elements of described fuel gas control device, described water conveying inhibitory control starting device D operates described oxidant gas control device;
Water conveying inhibitory control arresting stop D, after described water conveying inhibitory control starting device D operates described oxidant gas control device, if judge the hypervolia near described oxidant gas flow paths outlet by described decision maker B and/or D, then described water conveying inhibitory control arresting stop D makes described water carry promotion to control starting device D and again operates described fuel gas control device, and if judge that the water yield near described oxidant gas flow paths outlet is not too much by described decision maker B and/or D, then described water conveying inhibitory control arresting stop D stops described oxidant gas control device and continues the described fuel cell of operation.
20. fuel cell systems according to claim 1, is characterized in that, described fuel gas is not moist fuel gas.
The method of operation of 21. 1 kinds of fuel cells, described fuel cell has heap, described heap has monocell, described monocell comprises membrane electrode assembly, in described membrane electrode assembly, polymer dielectric film is clipped between pair of electrodes, and on the side of described membrane electrode assembly, be provided with oxidant gas flow paths, and fuel gas flow path is provided with on the opposite side of described membrane electrode assembly, described fuel gas flow path and described oxidant gas flow paths are arranged so that described fuel gas and described oxidant gas relative to each other flow along contrary direction on described membrane electrode assembly, described fuel gas flow path comprises fuel gas flow path entrance and fuel gas flow path outlet, and, described oxidant gas flow paths comprises oxidant gas flow paths entrance and oxidant gas flow paths outlet, it is characterized in that, the method of operation of described fuel cell comprises:
In I) do not have moist condition or II) under the temperature of described membrane electrode assembly is in the condition of at least 70 DEG C at least one condition, judge that whether the water yield near described oxidant gas flow paths entrance is not enough; And
In order to the uneven distribution of anti-sealing on battery surface, if it is determined that the water shortage near oxidant gas flow paths entrance, be then increased in the water yield near described oxidant gas flow paths entrance by increasing described fuel gas flow and/or reducing described fuel gas pressure.
The method of operation of 22. fuel cells according to claim 21, is characterized in that, the method for operation of described fuel cell also comprises:
Judge that whether the water yield near described oxidant gas flow paths outlet is not enough; And
If it is determined that the water yield near described oxidant gas flow paths entrance and/or the water shortage near the outlet of described oxidant gas flow paths, then reduce the water yield of being taken out of from described battery by described oxidant gas by reducing described oxidizer gas flow rate and/or increase described oxidant gas pressure and increase the water yield that can be transported to described fuel gas flow path entrance side from described oxidant gas flow paths outlet side.
The method of operation of 23. fuel cells according to claim 21 or 22, it is characterized in that, the method for operation of described fuel cell also comprises:
Measure the resistance value of whole described fuel cell; And
When 105% of the minimum value of the resistance measured in advance of the described monocell at each temperature that described resistance value exceedes in multiple temperature and/or described heap, judge the water shortage near described oxidant gas flow paths entrance and/or the water shortage near described oxidant gas flow paths outlet.
The method of operation of 24. fuel cells according to claim 21 or 22, it is characterized in that, the method for operation of described fuel cell also comprises:
Measure the voltage of whole described fuel cell; And
When 95% of the maximum of the voltage measured in advance of the described monocell at each temperature that described voltage is less than in multiple temperature and/or described heap, judge the hypervolia near described oxidant gas flow paths entrance and/or the hypervolia near described oxidant gas flow paths outlet.
The method of operation of 25. fuel cells according to claim 21 or 22, it is characterized in that, the method for operation of described fuel cell also comprises:
Measure the pressure drop flowing through the oxidant gas of described oxidant gas flow paths; And
When described pressure drop is less than 105% of the minimum value of the pressure drop of measuring in advance of the oxidant gas flowing through described oxidant gas flow paths, judge the water shortage near described oxidant gas flow paths entrance and/or the water shortage near described oxidant gas flow paths outlet.
The method of operation of 26. fuel cells according to claim 21 or 22, it is characterized in that, the method for operation of described fuel cell also comprises:
Measure the pressure drop flowing through the oxidant gas of described oxidant gas flow paths; And
When described pressure drop exceedes 105% of the maximum of the pressure drop of measuring in advance of the oxidant gas flowing through described oxidant gas flow paths, judge the hypervolia near described oxidant gas flow paths entrance and/or the hypervolia near described oxidant gas flow paths outlet.
The method of operation of 27. fuel cells according to claim 21 or 22, it is characterized in that, described fuel gas pressure is reduced to and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa.
The method of operation of 28. fuel cells according to claim 21 or 22, it is characterized in that, the stoichiometric proportion of described oxidant gas is reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0.
The method of operation of 29. fuel cells according to claim 21 or 22, it is characterized in that, the stoichiometric proportion of described fuel gas increases to and is more than or equal to 1.0 and is less than or equal in the scope of 10.
The method of operation of 30. fuel cells according to claim 21 or 22, it is characterized in that, described oxidant gas pressure increases to and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa.
The method of operation of 31. fuel cells according to claim 21 or 22, it is characterized in that, the method for operation of described fuel cell also comprises:
If it is determined that the water shortage near described oxidant gas flow paths entrance, then the stoichiometric proportion of described fuel gas increases to and is more than or equal to 1.0 and is less than or equal in the scope of 10 by one or many, and/or is reduced to by described fuel gas pressure and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa;
Then, after judging the water shortage near described oxidant gas flow paths outlet, stop controlling described fuel gas;
Then, the stoichiometric proportion of described oxidant gas is reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0 by one or many, and/or is increased to by described oxidant gas pressure and be more than or equal to atmospheric pressure and be less than or equal in the scope of 0.3MPa;
Then, after judging the hypervolia near described oxidant gas flow paths outlet, stop controlling described oxidant gas;
Then, if it is determined that the water shortage near described oxidant gas flow paths entrance, then again start to control described fuel gas, and if judge that the water yield near described oxidant gas flow paths entrance is not not enough, then continue the described fuel cell of operation.
The method of operation of 32. fuel cells according to claim 21 or 22, it is characterized in that, the method for operation of described fuel cell also comprises:
If it is determined that the water shortage near described oxidant gas flow paths entrance, then the stoichiometric proportion of described oxidant gas is reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0 by one or many, and/or is increased to by described oxidant gas pressure and be more than or equal to atmospheric pressure and be less than or equal in the scope of 0.3MPa;
Then, after judging the hypervolia near described oxidant gas flow paths outlet, stop controlling described oxidant gas;
Then, the stoichiometric proportion of described fuel gas increases to and is more than or equal to 1.0 and is less than or equal in the scope of 10 by one or many, and/or is reduced to by described fuel gas pressure and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa;
Then, after judging the water shortage near described oxidant gas flow paths outlet, stop controlling described fuel gas;
Then, if it is determined that the water shortage near described oxidant gas flow paths entrance, then again start to control described oxidant gas, and if judge that the water yield near described oxidant gas flow paths entrance is not not enough, then continue the described fuel cell of operation.
The method of operation of 33. fuel cells according to claim 21 or 22, it is characterized in that, the method for operation of described fuel cell also comprises:
The stoichiometric proportion of described fuel gas increases to and is more than or equal to 1.0 and is less than or equal in the scope of 10 by one or many, and/or is reduced to by described fuel gas pressure and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa;
Then, after judging the water shortage near described oxidant gas flow paths outlet, stop controlling described fuel gas;
Then, the stoichiometric proportion of described oxidant gas is reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0 by one or many, and/or is increased to by described oxidant gas pressure and be more than or equal to atmospheric pressure and be less than or equal in the scope of 0.3MPa;
Then, after judging the hypervolia near described oxidant gas flow paths outlet, stop controlling described oxidant gas;
Then, the stoichiometric proportion of described fuel gas is increased to and is more than or equal to 1.0 and is less than or equal in the scope of 10, and/or described fuel gas pressure is reduced to is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa; And
Then, if it is determined that the water shortage near described oxidant gas flow paths outlet, then again start to control described oxidant gas, and if judge that the water yield near described oxidant gas flow paths outlet is not not enough, then stop controlling described fuel gas and continue the described fuel cell of operation.
The method of operation of 34. fuel cells according to claim 21 or 22, it is characterized in that, the method for operation of described fuel cell also comprises:
The stoichiometric proportion of described oxidant gas is reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0 by one or many, and/or is increased to by described oxidant gas pressure and be more than or equal to atmospheric pressure and be less than or equal in the scope of 0.3MPa;
Then, after judging the hypervolia near described oxidant gas flow paths outlet, stop controlling described oxidant gas;
Then, the stoichiometric proportion of described fuel gas increases to and is more than or equal to 1.0 and is less than or equal in the scope of 10 by one or many, and/or is reduced to by described fuel gas pressure and is more than or equal to atmospheric pressure and is less than or equal in the scope of 0.3MPa;
Then, after judging the water shortage near described oxidant gas flow paths outlet, stop controlling described fuel gas;
Then, the stoichiometric proportion of described oxidant gas is reduced to and is more than or equal to 1.0 and is less than or equal in the scope of 3.0, and/or described oxidant gas pressure is increased to be more than or equal to atmospheric pressure and be less than or equal in the scope of 0.3MPa; And
Then, if it is determined that the hypervolia near described oxidant gas flow paths outlet, then again start to control described fuel gas, and if judge that the described water yield is not too much, then stop controlling described oxidant gas and continue the described fuel cell of operation.
CN201510726171.7A 2008-03-26 2009-03-26 The operating method of fuel cell system and fuel cell Expired - Fee Related CN105186018B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2008080361 2008-03-26
JP2008-080361 2008-03-26
JP2008-171365 2008-06-30
JP2008171365A JP2009259758A (en) 2008-03-26 2008-06-30 Fuel cell system and operating method of fuel cell
CN200980100116XA CN101933183A (en) 2008-03-26 2009-03-26 Fuel cell system and operating method of a fuel cell

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN200980100116XA Division CN101933183A (en) 2008-03-26 2009-03-26 Fuel cell system and operating method of a fuel cell

Publications (2)

Publication Number Publication Date
CN105186018A true CN105186018A (en) 2015-12-23
CN105186018B CN105186018B (en) 2018-09-11

Family

ID=40846391

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201510726171.7A Expired - Fee Related CN105186018B (en) 2008-03-26 2009-03-26 The operating method of fuel cell system and fuel cell
CN200980100116XA Pending CN101933183A (en) 2008-03-26 2009-03-26 Fuel cell system and operating method of a fuel cell

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN200980100116XA Pending CN101933183A (en) 2008-03-26 2009-03-26 Fuel cell system and operating method of a fuel cell

Country Status (7)

Country Link
US (1) US9991529B2 (en)
EP (1) EP2269257B1 (en)
JP (2) JP2009259758A (en)
KR (1) KR101239702B1 (en)
CN (2) CN105186018B (en)
CA (1) CA2696050C (en)
WO (1) WO2009118649A1 (en)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011018856A1 (en) * 2009-08-14 2011-02-17 トヨタ自動車株式会社 Method for controlling water content in fuel cell and fuel cell system
JP5625469B2 (en) * 2010-05-06 2014-11-19 トヨタ自動車株式会社 Fuel cell system
WO2012101819A1 (en) 2011-01-28 2012-08-02 トヨタ自動車株式会社 Fuel cell system
CN102986070B (en) * 2011-01-28 2015-06-24 丰田自动车株式会社 Fuel cell system
JP5741922B2 (en) * 2011-04-13 2015-07-01 トヨタ自動車株式会社 Fuel cell drying control method
JP5678276B2 (en) 2011-04-18 2015-02-25 トヨタ車体株式会社 Fuel cell
DE102011113010A1 (en) * 2011-09-09 2013-03-14 Daimler Ag Method for operating a fuel cell system
FR2985523B1 (en) * 2012-01-06 2014-11-28 Commissariat Energie Atomique POROUS ELECTRODE FOR PROTON EXCHANGE MEMBRANE
US20150207158A1 (en) * 2012-07-23 2015-07-23 Toyota Jidosha Kabushiki Kaisha Fuel cell system and its operating method
TWI458996B (en) 2012-12-07 2014-11-01 Ind Tech Res Inst Fuel cell failure prediction apparatus and method
KR101438617B1 (en) * 2012-12-28 2014-09-05 현대자동차 주식회사 Operating method of fuel cell system
WO2015136677A1 (en) * 2014-03-13 2015-09-17 日産自動車株式会社 Fuel cell system
JP6442987B2 (en) * 2014-10-31 2018-12-26 日産自動車株式会社 Fuel cell system
US10020523B2 (en) 2015-03-27 2018-07-10 Nissan Motor Co., Ltd. Fuel cell system and control method for fuel cell system
US10173613B2 (en) * 2015-08-18 2019-01-08 GM Global Technology Operations LLC System and method for monitoring a state of charge of a battery
JP6477896B2 (en) * 2015-09-11 2019-03-06 日産自動車株式会社 Fuel cell system control apparatus and fuel cell system control method
DE102017206729B4 (en) * 2016-04-29 2022-11-24 Ford Global Technologies, Llc Method for operating a fuel cell system
DE102016207806A1 (en) * 2016-05-04 2017-11-09 Bayerische Motoren Werke Aktiengesellschaft Method for operating a fuel cell system
KR102496644B1 (en) * 2017-10-17 2023-02-07 현대자동차주식회사 Fuel cell system and control method thereof
US10784527B2 (en) * 2017-12-19 2020-09-22 GM Global Technology Operations LLC System and method for MEA conditioning in a fuel cell
JP6974205B2 (en) * 2018-02-09 2021-12-01 株式会社Soken Fuel cell system
DE102021202053A1 (en) 2021-03-03 2022-09-08 Vitesco Technologies GmbH Diagnosis of the moisture condition of a PEM fuel cell stack
KR20240048800A (en) 2022-10-07 2024-04-16 국방과학연구소 Fuel cell system

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1340221A (en) * 1999-01-12 2002-03-13 泰勒戴尼能源系统公司 Method and apparatus for maintaining neutral water balance in a fuel cell system
CN1503998A (en) * 2001-03-06 2004-06-09 ���＼�й�ҵ��ʽ���� Solid polymer electrolyte fuel cell assembly, fuel cell stank, and method of supplying reaction gas ni fuel cell
US20060166058A1 (en) * 2005-01-25 2006-07-27 Denso Corporation Fuel cell system ensuring stability of operation
JP2007220322A (en) * 2006-02-14 2007-08-30 Nissan Motor Co Ltd Fuel cell system

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5260143A (en) 1991-01-15 1993-11-09 Ballard Power Systems Inc. Method and apparatus for removing water from electrochemical fuel cells
JP2001006698A (en) 1999-06-23 2001-01-12 Fuji Electric Co Ltd Solid polymer electrolyte fuel cell and manufacture of its diffusion layer
US6500579B1 (en) * 1999-08-19 2002-12-31 Mitsubishi Denki Kabushiki Kaisha Fuel cell structure
JP2001148253A (en) * 1999-11-22 2001-05-29 Matsushita Electric Ind Co Ltd High polymer electrolyte type fuel cell and its operation method
US6376111B1 (en) * 2000-01-25 2002-04-23 General Motors Corporation System and method for controlling the humidity level of a fuel cell
JP2002352827A (en) * 2001-05-22 2002-12-06 Denso Corp Fuel cell system
JP3736475B2 (en) 2002-02-26 2006-01-18 日産自動車株式会社 Fuel cell
JP4013218B2 (en) * 2002-04-23 2007-11-28 独立行政法人 宇宙航空研究開発機構 Solid polymer electrolyte fuel cell
US20040096709A1 (en) * 2002-11-15 2004-05-20 Darling Robert M. Fuel cell system with a dry cathode feed
JP4639680B2 (en) * 2003-09-05 2011-02-23 株式会社デンソー Fuel cell system
US7781118B2 (en) 2004-02-09 2010-08-24 Gm Global Technology Operations, Inc. Fuel cell flooding detection
ITMI20042247A1 (en) 2004-11-19 2005-02-19 Nuvera Fuel Cells Europ Srl ELECTRIC GENERATION SYSTEM INCLUDING FUEL CELLS WITH MEMBRANE POWERED BY DRIED GAS
US7862935B2 (en) 2005-05-17 2011-01-04 Gm Global Technology Operations, Inc. Management via dynamic water holdup estimator in a fuel cell
US20070264551A1 (en) * 2006-03-16 2007-11-15 Atsushi Matsunaga Membrane/Electrode Assembly and Fuel Cell
JP5168848B2 (en) 2006-08-10 2013-03-27 日産自動車株式会社 Fuel cell system
JP4548453B2 (en) * 2007-07-04 2010-09-22 トヨタ自動車株式会社 FUEL CELL SYSTEM AND CONTROL DEVICE FOR FUEL CELL SYSTEM

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1340221A (en) * 1999-01-12 2002-03-13 泰勒戴尼能源系统公司 Method and apparatus for maintaining neutral water balance in a fuel cell system
CN1503998A (en) * 2001-03-06 2004-06-09 ���＼�й�ҵ��ʽ���� Solid polymer electrolyte fuel cell assembly, fuel cell stank, and method of supplying reaction gas ni fuel cell
US20060166058A1 (en) * 2005-01-25 2006-07-27 Denso Corporation Fuel cell system ensuring stability of operation
JP2007220322A (en) * 2006-02-14 2007-08-30 Nissan Motor Co Ltd Fuel cell system

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
QIANGU YAN ET AL，: "Investigation of water transport through membrane in a PEM fuel cell by water balance experiments", 《JOURNAL OF POWER SOURCES》 *

Also Published As

Publication number Publication date
WO2009118649A1 (en) 2009-10-01
JP2009259758A (en) 2009-11-05
EP2269257B1 (en) 2014-02-26
CN101933183A (en) 2010-12-29
JP2010538415A (en) 2010-12-09
EP2269257A1 (en) 2011-01-05
US9991529B2 (en) 2018-06-05
CA2696050C (en) 2013-09-10
KR101239702B1 (en) 2013-03-06
US20110200896A1 (en) 2011-08-18
JP5104950B2 (en) 2012-12-19
CN105186018B (en) 2018-09-11
KR20100028671A (en) 2010-03-12
CA2696050A1 (en) 2009-10-01

Similar Documents

Publication Publication Date Title
CN105186018A (en) Fuel cell system and operating method of a fuel cell
Baxter et al. Methanol fuel cell model: anode
US9281531B2 (en) Electrochemical system having multiple independent circuits
US20060199055A1 (en) Electrochemical Cell Stacks and Use Thereof
KR100528340B1 (en) Liguid fuel mixing apparatus and fuel cell apparatus adopting the same
CN101803086B (en) Electrochemical systems having multiple independent circuits
US20080138668A1 (en) Direct methanol fuel cell
JPH09283157A (en) Fuel cell, manufacture of fuel cell, composite gas separator, and its manufacture
US20090047561A1 (en) Method of making fuel cell diffusion layer and fuel cell diffusion layer
CN101427409A (en) Method and apparatus for measuring crossover loss of fuel cell
US6682835B2 (en) Method and apparatus for increasing the operational efficiency of a fuel cell power plant
CN102986070B (en) Fuel cell system
JP4462502B2 (en) Cathode electrode structure for fuel cell and fuel cell having the same
CN101356678A (en) Ion conductor and fuel cell
KR100619193B1 (en) Fuel cell and separator for fuel cell
JP4372370B2 (en) Fuel cell
US20040115500A1 (en) Polymer electrolyte fuel cell and power-generating system with polymer electrolyte fuel cells
JP4340417B2 (en) Polymer electrolyte fuel cell
JP3380805B2 (en) Composite gas separator for fuel cells
US20060115696A1 (en) Hydrogen gas humidity control apparatus, fuel cell, hydrogen gas humidity controlling method, and humidity control method for fuel cell
CN101978539A (en) Fuel cell unit, fuel cell stack, and electronic device
JP2009026539A (en) Membrane electrode assembly for fuel cell
JP2017510038A (en) Optimal fuel cell
JP2021128866A (en) Fuel cell system
JP2004253359A (en) Fuel cell and humidity control method of fuel cell

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180911

CF01 Termination of patent right due to non-payment of annual fee